Gels for force gauging

ABSTRACT

For effective plaque removal, a combination of a gel force gauging component and a plaque removing gel component are employed to prevent tooth and gum damage over gel rigidity range of from about 75 gram Bloom to about 300 gram bloom.

RELATED APPLICATIONS

[0001] This application is a continuation-in-part of the followingapplications Ser. No. 10/420,089 filed Apr. 21, 2002; Ser. No.10/420,487 filed Apr. 21, 2003; Ser. No. 10/420,488 filed Apr. 21, 2003;Ser. No. 10/420,490 filed Apr. 21, 2003; Ser. No. 10/420,491 filed Apr.21, 2003; Ser. No. 10/420,492 filed Apr. 21, 2003; Ser. No. 10/420,493filed Apr. 21, 2003; Ser. No. 10/896,047 filed Jun. 30, 2001; Ser. No.10/273,828 filed Oct. 17, 2002; Ser. No. 10/334,542 filed Dec. 31, 2002;Ser. No. 10/299,073 filed Nov. 18, 2002; Ser. No. 10/199,364 filed Jul.20, 2002; Ser. No. 09/721,213 filed Nov. 21, 2001; Ser. No. 10/199,361filed Jul. 20, 2002; Ser. No. 10/199,362 filed Jul. 20, 2002; Ser. No.10/199,363 filed Jul. 20, 2002; Ser. No. 09/517,230, filed Mar. 2, 2000;Ser. No. 09/412,886, filed Oct. 5, 1999; Ser. No. 09/285,809, filed Apr.1, 1999; Ser. No. 09/274,498, filed Mar. 23, 1999; Ser. No. 08/130,545,filed Aug. 8, 1998; Ser. No. 08/984,459, filed Dec. 3, 1997; Ser. No.08/909,487, filed Jul. 12, 1997; Ser. No. 08/863,794, filed May 27,1997; PCT/US97/17534, filed Sep. 30, 1997; U.S. Ser. No: 08/719,817filed Sep. 30, 1996; U.S. Ser. No: 08/665,343 filed Jun. 17, 1996 whichis a Continuation-in-part of U.S. Ser. No: 08/612,586 filed Mar. 8, 1996(now U.S. Pat. No. 6,552,109); PCT/US94/04278 filed Apr. 19, 1994(published May 26, 1995 No. WO95/13851); PCT/US94/07314 filed Jun. 27,1994 (published Jan. 4, 1996 No. WO 96/00118); Ser. No. 08/288,690 filedAug. 11, 1994; Ser. No. 08/581,188 filed Dec. 29, 1995; Ser. No.08/581,191 filed Dec. 29, 1995; Ser. No. 08/581,125 filed Dec. 29, 1995now U.S. Pat. No. 5,962,527. In turn U.S. Ser. Nos. 581,188; 581,191;and 581,125 (now U.S. Pat. No. 5,962,572) are continuation-in-parts ofthe following applications: Ser. Nos.: 288,690, filed Aug. 11, 1994,PCT/US94/07314 filed Jun. 27, 1994 (CIP of PCT/US 94/04278, filed Apr.19, 1994). The subject matter contained in the related applications andpatents are specifically incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention is directed to oral health care.

DESCRIPTION OF THE DRAWINGS

[0003]FIGS. 1a-3 j, and 6 b-6 g are representative top views of deepsurface patterned gel articles suitable for use on a finger, with ahandle, or on an electric head.

[0004]FIGS. 3q-4 n are representative crossection views of articles ofbristles and gels.

[0005]FIGS. 4o-5 c, 5 h-5 i, and 5 k are representative crossectionviews of composites gel articles for force gauging and plaque removal.

[0006]FIGS. 5d-5 g, 5 j, 5 l, 5 n-6 a, and 6 h are representativecrossection views of deep patterned and structured gel shaped articles.

[0007] FIGS. 7-7 d, 8, 9 a-9 g are representative crossection of gelcomposites.

[0008]FIG. 10 shows gel sheets and strips.

[0009]FIGS. 11a-13 b are representative crossection views gel fingerarticles.

[0010]FIGS. 15a-15 k, 15 m, 15 n are representative views of gelarticles for use on a handle, a finger and electric head.

DETAILED DESCRIPTION OF THE INVENTION

[0011] In the Journal of Clinical Periodontology, volume 30; 409-413McCracken et al., report that brushing time and brushing force havesignificant effects upon the level of plaque removal by a poweredtoothbrush, and at 120 seconds brushing time the improvement in plaqueremoval with forces in excess of 150 gram was negligible. The sameconclusion is applicable to brushing time of 180 seconds, although therewas a trend towards greater plaque removal when a brushing force of 300gram was used.

[0012] According to the Vancouver Sun, Professor Peter Heasman said theideal is to spend two minutes twice a day brushing with a pressureequivalent to holding an orange. “You don't have to scrub and you don'thave to work away with Olympian force,” “People who brush their teethfor longer and harder than is necessary may not be making them anycleaner, and could be causing permanent damage.”

[0013] The Trinity Mirror reported “It is virtually impossible for theaverage user to gauge how much pressure they are applying during theirbrushing regime. “For example, the force you apply to your toothbrushcould be quite light but the pressure will be much greater because youare applying that force to a very small area,” Professor Heasman said.

[0014] Barbara Lantin of London reported that Professor Heasman said:“The most significant causative factor is the incorrect use of thetoothbrush.” In the four-week study, 12 people tested 16 methods ofbrushing, taking 30 seconds to three minutes and applying pressureequivalent to between 75 grams and 300 grams. “Time was not the biggestissue.” “People can take three minutes or more, but if they combine itwith too much force, it can cause problems. Relatively light force,equivalent to 150 grams, removes plaque. Going beyond that can causewear on the teeth that looks as if somebody has taken a chisel to them,and can contribute to receding gums.

[0015] Martin Wainwright of the Guardian reported that getting thepressure right was harder and might prove a long, error-strewn exercise.“It is virtually impossible for the average user to gauge how muchpressure they are applying,” said Proof Heasman. His best advice was tocompare the ideal pressure, 150 grams, with the weight of an orange.Holding an orange in one hand and brushing with the other is impracticaland possibly embarrassing, however, the study accepts. “It's a genuineproblem. You have to brush your teeth reasonably long and hard to getrid of the harmful plaque which causes dental diseases.” said ProofHeasman. These comments by Professor Heasman as posted recently on theInternet and cited article are herein incorporated by reference.

[0016] The virtual impossibility for an average toothbrush user to gaugethe brush pressure (equivalent to the weight of an orange) applied tothe teeth and gum while brushing is a genuine problem according toProfessor Heasman, which can only be overcome by a long, error-strewnexercise. Up to the time of the instant invention, a solution to theforce gauging problem had not been realized.

[0017] The force gauging problem solving invention comprises a handlemeans for transferring one or more motion forces to a plaque removingmeans for contact with a surface having attached at one end of saidhandle means a force gauging means which is attached to said plaqueremoving means, said force gauging means for gauging said motion forcesbetween said plaque removing means and said surface.

[0018] The uses of elastic invention gels, and invention gel compositesas means for force gauging and plaque removal are new. Gels made fromhigh viscosity SEEPS block copolymers exhibit greater tear and fatigueresistance. Such uses of tear resistant and fatigue resistant gels arealso new. Without such resistant gels, the force gauging and plaqueremoving gel components, and gel elements of such composites wouldreadily fail during active use.

[0019] The plaque removing gel components and gel force gaugingcomponents of the invention can be made from silicone, polyurethane,SEBS, SEPS, SEEPS, SBS, SBEBS, SEB/EPS gels of selected rigidities.Various useful gel compositions are disclosed in my patents andapplication as follows: U.S. Pat. Nos. 20020188057; 6,552,109 B1,6,420,475, 6,161,555, 6,333,374; 6,324,703; 6,148,830; 6,117,176;6,050,871; 6,033,283, 5,962,572, 5,938,499, 5,884,639, 8597, 5,760,117,5,655,947, 5,633,286, 5,508,334, 5,624,294, 5,508,334, 5,475,890,5,336,708, 5,334,646; 5,324,222, 5,329,723, 5,262,468, 5,153,254,PCT/US97/17534, PCT/US94/04278 and PCT/US94/0731 which are incorporatedherein by reference. The invention selective gels can be made to anypredetermined selected “gel rigidity”. As used herein, the term “gelrigidity” in gram Bloom is determined by the gram weight required todepress a gel a distance of 4 mm with a piston having a cross-sectionalarea of 1 square centimeter at 23° C.

[0020] The problem identified by Professor Heasman's study is solved bya plaque removing article comprising: a handle 4 having attached at oneend of said handle, a gel composite of at least one gel force gaugingcomponent 5 and a brush member holding base 3, said gel force gaugingcomponent 5 being attached to said handle 4 and attached to said brushmember holding base 3 for holding a brush member 1 opposite said gelforce gauging component 5, wherein said gel force gauging component 5can be made from a gel composition having a selected gel rigidity ofabout 75 gram Bloom to about 300 gram Bloom.

[0021] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle 4, abrush member holding base 3, said brush member holding base 3 beingattached to at least one gel force gauging component 2 and holding abrush member 1 opposite said handle 4, wherein said gel force gaugingcomponent 2 is made from a gel composition having a selected gelrigidity of about 75 gram Bloom to about 300 gram Bloom.

[0022] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle 4, agel composite of at least one gel force gauging component 5 and a brushmember holding base 3, said brush member holding base 3 being attachedto at least one gel force gauging component 2 and holding a brush member1 opposite said handle 4, wherein said gel force gauging component 2 ismade from a gel composition having a selected gel rigidity of about 75gram Bloom to about 300 gram Bloom.

[0023] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle 4, acomposite of at least one gel force gauging component 5 and at least oneplaque removing gel component 6, wherein said gel force gaugingcomponent is made from a gel composition having a selected gel rigidityof from about 75 gram Bloom to about 300 gram Bloom and said plaqueremoving gel component is made from a gel composition having a selectedgel rigidity of from about 150 gram Bloom to about 1,250 gram Bloom.

[0024] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle, acomposite comprising at least one gel force gauging component 5 and aplaque removing textural component 7, wherein said gel force gaugingcomponent 5 is made from a gel composition having a selected gelrigidity of from about 75 gram Bloom to about 300 gram Bloom and saidplaque removing textural component 7 is made from a woven or non wovenfabric of webs, loops, and fibers, and a sponge.

[0025] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle 4, aplaque removing gel component 6, wherein said plaque removing gelcomponent is made from a gel composition having a selected gel rigidityof from about 75 gram Bloom to about 300 gram Bloom.

[0026] The problem is also solved by a plaque removing articlecomprising: a handle 4 having attached at one end of said handle 4, agel composite of at least one gel force gauging component 5 which isattached to at least one a plaque removing gel component 6, wherein saidgel force gauging component 5 is made from a gel composition having aselected gel rigidity of from about 75 gram Bloom to about 300 gramBloom, and said plaque removing gel component 6 is made from a gelcomposition having a selected gel rigidity of from about 150 gram Bloomto about 1,250 gram Bloom.

[0027] The problem is also solved by a plaque removing articlecomprising: a handle 4 attached to at least one plaque removing gelcomponent 6, said plaque removing gel component having an array ofprotruded shaped grooves, stems, tips, wedges, points, angular edges,corners, and sides.

[0028] The problem is also solved by a plaque removing articlecomprising: a handle 4 attached to at least one plaque removing gelcomponent 6, said plaque removing gel component 6 having a deeppatterned surface for effective engaging plaque from off the surface ofa tooth.

[0029] The problem is also solved by a plaque removing articlecomprising: at least one plaque removing gel component 6, said plaqueremoving gel component 6 attached to a gel force gauging component 5having a hollow member 10 sized for receiving and holding a finger, saidgel force gauging component 5 being surrounded by said a plaque removinggel component 6, wherein said gel force gauging component is made from agel composition having a selected gel rigidity of from about 75 gramBloom to about 300 gram Bloom and said plaque removing gel component ismade from a gel composition having a selected gel rigidity of from about150 gram Bloom to about 1,250 gram Bloom.

[0030] The problem is also solved by a plaque removing articlecomprising: a gel force gauging component 5 having a hollow member 10sized for receiving and holding a finger, said gel force gaugingcomponent 5 being surrounded by a plaque removing textural component 9,wherein said gel force gauging component 5 is made from a gelcomposition having a selected gel rigidity of from about 75 gram Bloomto about 300 gram Bloom and said plaque removing textural component ismade from a woven or non woven fabric of webs, loops, and fibers, and asponge.

[0031] The problem is also solved by a plaque removing articlecomprising: a gel force gauging component 5 having a hollow member 10sized for receiving and holding a finger, said gel force gaugingcomponent 5 being surrounded by a plaque removing gel component 6,wherein said gel force gauging component 5 is made from a gelcomposition having a selected gel rigidity of from about 75 gram Bloomto about 300 gram Bloom and said plaque removing gel component is madefrom a gel composition having a selected gel rigidity of from about 150gram Bloom to about 1,250 gram Bloom.

[0032] The plaque removing gel component and gel force gauging componentcan be made from a gel comprising: (i) 100 parts by weight of one or amixture of two or more of a hydrogenated styrene isoprene/butadieneblock copolymer(s) and from (ii) about 300 to about 1,600 parts byweight of a plasticizing oil; and in combination with or without (iii) aselected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene.

[0033] The plaque removing gel component and gel force gauging componentcan also be made from a gel comprising: (i) 100 parts by weight of oneor a mixture of two or more of a hydrogenated styrene isoprene/butadieneblock copolymer(s) and from (ii) about 300 to about 1,600 parts byweight of a plasticizing oil; and in combination with or without (iii) aselected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer.

[0034] The plaque removing gel component and gel force gauging componentcan also be made from a gel comprising:(i) 100 parts by weight of one ora mixture of two or more of a hydrogenated styrene block copolymer(s)with 2-methyl-1,3-butadiene and 1,3-butadiene and (ii) from about 300 toabout 1,600 parts by weight of an plasticizing oil; in combination withor without (iii) a selected amount of one or more selected polymer orcopolymer selected from the group consisting ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,branched, star-shaped, or multiarm copolymer; and n is an integergreater than one.

[0035] The plaque removing gel component and gel force gauging componentcan also be made from a gel comprising:(i) 100 parts by weight of one ora mixture of two or more of a hydrogenated styrene isoprene/butadieneblock copolymer(s), wherein at least one of said block copolymer is ahigh viscosity copolymer having a viscosity value at 5 weight percentsolution in toluene at 30° C. of about 90 cps and higher whichcorresponds to a viscosity at 10 weight percent of about 5800 cps andhigher which corresponds to a viscosity at 20 weight percent solidssolution in toluene at 25° C. of at about 80,000 cps and higher, and(ii) from about 300 to about 1,600 parts by weight of an plasticizingoil, and in combination with or without (ii) a selected amount of one ormore polymers or copolymers of poly(styrene-butadiene-styrene),poly(styrene-butadiene), poly(styrene-isoprene-styrene),poly(styrene-isoprene), poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, branched,radial, star-shaped, or multiarm copolymer; and n is an integer greaterthan one.

[0036] The plaque removing gel component and gel-force gauging componentcan also be made from a gel comprising a hydrogenated styrene blockcopolymer can be one or more of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from less then about 75 gram Bloom toabout 300 gram Bloom and higher.

[0037] The plaque removing gel component and gel force gauging componentcan also be made from a gel comprising a hydrogenated styrene blockcopolymer can be one or more of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from about 75 gram Bloom to about 300gram Bloom, wherein a source of said hydrogenatedpoly(styrene-isoprene/butadiene-styrene) block polymer being a Septon®poly(styrene-ethylene-ethylene-propylene-styrene) block copolymer.

[0038] The plaque removing gel component and gel force gauging componentcan also be made from a gel comprising a hydrogenated styrene blockcopolymer can be one or more of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from about 75 gram Bloom to about 300gram Bloom, wherein said one or more (i) block copolymer(s) can bepoly(styrene-ethylene-ethylene-propylene-styrene) and a source of saidblock copolymers being Septon® 4033, Septon® 4044, Septon® 4045 andSepton® 4055, Septon® 4077, and Septon® 4099.

[0039] With reference to the representative Figures, the invention canbe depicted by:(i) one or more plaque removing components 1 incombination with one or more gel force gauging components (GFGC) 2 ofFIGS. 3u-4 b, 4 i-4 n; (ii) one or more plaque removing components 1, 7,8, and 9 in combination with one or more GFGC 5 of FIGS. 3q-3 t, 4 u-4z, 5 a-5 c, 5 h-5 i, 5 k, 11 a, 11 c-13 b; (iii) one or more plaqueremoving gel components (PRGC) 6 of FIGS. 1a-3 j, 4 o, 4 t, 5 d-5 g, 5j, 5L, 6 a, 6 h, 11 b, 11 c, 12 c, 15 a-15 k in combination with orwithout one or more GFGC 5, the PRGC.

[0040] The invention selective gels can be formed of almost anypatterned or protruded structures as represented in the FIGS 1 a-3 j, 4o, 4 t, 5 d-5 g, 5 j, 5L, 6 a, 6 h, 11 b, 11 c, 12 c, 15 a-15 k, 15 m,15 n such as a matrix or array of grooves, stems, tips, wedges, points,angular corners, edges or sides and the like.

[0041] For toothbrushes 1, the designed brushing surface areas can rangefrom less than 1.0 square centimeter to 3.0 square centimeter or higher.On average, any active engaging depressed depth (length of the bristlesof a toothbrush that can be depress or deformed or pushed aside from itsdesigned configuration or bent away from its designed shape) can be lessthan 1 mm to greater than 4 mm during brushing. Likewise, on average theactive engaging surface area of the teeth and gum in contact with anaverage surface area of bristles of a toothbrush at any one time can beless than 1 square centimeter to greater than about 3 square centimeterdepending on the user's applied force. Smaller toothbrushes foryoungsters are designed to cover less surface area than toothbrushes foradults. Knowing the parameters of a toothbrush's maximum and minimumdesigned active depressed depth for any user, its average activebrushing area that is most likely applied against the teeth or gum atany one time by any user (a light, medium, or heavy brusher), then thegel rigidity in gram Bloom can be determined by the gram weight requiredto depress a gel the designed depressed depth “X” in mm with a designedbrushing cross-sectional area “Y” in square centimeter, where “X” for alight brusher can range from less than about 0.5 mm to about 2.0 mm, fora medium brusher, “X” can range from about 2.0 mm to about 3.5 mm, andfor a heavy brusher, “X” can range from about 3.5 mm to about 5 mm.

[0042] Thus, “X” can have values of less than 0.25 mm to greater thanabout 6.0 mm which range include all values in between, typically suchas 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 mm. The designedbrushing cross-sectional area, Y can be about 0.5, 1, 1.5, 2, 2.5, 3, to3.5 or greater. A gel's rigidity in gram Bloom can therefore be selectedto match the design parameters X and Y values. The parameters weight todepress a gel X mm, and surface area Y in cm can be preselected andpredetermined when designing the GFGC and the PRGC of the invention.

[0043] Correspondingly, suitable gel rigidities “R₁” of the gels formingthe (GFGC) 2 of FIGS. 3u-4 b, 4 i-4 n and 5 of FIGS. 3q-3 t, 4 u-4 z, 5a-5 c, 5 h-5 i, 5 k, 11 a, 11 c-13 b can range from less than about 75gram Bloom to greater than 1,000 gram Bloom. Suitable gel rigiditiesare: 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86,87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 90, 91, 92, 93, 94, 95,96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110,120, 130, 14, 150, 16, 170, 180, 190, 200, 220, 240, 260, 280, 300, 320,360, 420, 460, 480, 520, 550, 580, 620, 650, 680, 720, 750, 780, 820,850, 880, 920, 950, 980, 1,000, and 1,250 including all rigidities inbetween such rigidities.

[0044] Correspondingly, suitable gel rigidities “R₂” of one or moreplaque removing gel components (PRGC) 6 of FIGS. 1a-3 j, 4 o, 4 t, 5 d-5g, 5 j, 5L, 6 a, 6 h, 11 b, 11 c, 12 c, 15 a-15 k, 15 m, 15 n can rangefrom less than about 75 gram Bloom to greater than 300 gram Bloom.Suitable gel rigidities are: 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80,81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98,90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105,106, 107, 108, 109, 110, 120, 130, 14, 150, 16, 170, 180, 190, 200, 220,240, 260, 280, 300, 320, 360 including all rigidities in between suchrigidities.

[0045] The plaque removing components 1, 6 (PRGC of patterned, grooved,stemmed, tipped, pointed, angled, cornered, wedged, or edged), 7, 8, 9,are of suitable dimensions of depth, length, and width to be applied incontact with full mouth and interproximal sites for effective plaquereduction and removal over the facial and lingual-palatal surfaces.

[0046] The bristles 1 is attached to the brush base 3 which is attachedto GFGC 5 which is attached to handle 4 (full length not shown). TheGFGC 2 can also be attached to brush base 3. Force gauging gel component2 and 5 can be of the same or different rigidity. Plaque removingcomponents 7, 8, 9 can be attached to GFGC 5. The GFGC 5 can be attachedto handle 4. The plaque removing gel component (PRGC) 6 of FIGS. 4o, 5d, 5 e, 5 f, 5 j, 5L, 6 a, 6 h, 15 a-15 k can be attached to the GFGC 5.The GFGC 2 can be patterned to any degree of depth to reach theinterproximal sites as well as accommodate the smooth surface sitesincluding areas of gingivitis buildup. The invention PRGC is suitablefor detaching plaque at the lingual and approximal vestibular surfaces;the front teeth and premolars, incisor and molar sites. The active PRGCcan be structured gel shapes with pointed tips, flat and slanted edges,cones, bar and cubed corner and edges shown in FIGS. 15a-15 k. One ormore of the various shapes can be combined on one PRGC surface. The PRGCshapes can have dimensions and separations from one another of about andin between ¼, ⅓, ½ to less than 1 unit of the width of the average sizedtooth for effective plaque removal.

[0047] The shaped PRGC structures of FIGS. 15a-15 k, 15 n, 15 n can alsobe made into sheets of any desired size for wrapping around a finger andinsertion into the mouth for cleaning the teeth and gum. Additionally,such sheets by themselves or made into composites with any desirableM_(n) substrates for cleaning or polishing of any desired surfaces,including high gloss surfaces such as glass,metal, ceramic,semiconductor surfaces. The sheets can be used in combination with apolishing slurry or paste medium for polishing semiconductor wafers.

[0048] Other materials useful for plaque removal components 7, 8, and 9in combination with GFGC 5 which materials include fabrics, cloths,fibers, webbing, and sponges.

[0049] The progressive deformation response by gel rigidities R₂ tops,wedges, tips and other of the structured gel shapes of FIGS. 15a-15 k(useful as PRGC in the configuration shown in FIGS. 5f, 5 j, 5L, and 13c) to applied increase forces produce more deformations in adjacent topsand tips, thereby transferring the added force over a greater andgreater surface area of engaged tops and tips while keeping the pressurewithin the maximum designed gram Bloom rigidity of the overall gel bodyof the PRGC.

[0050] Likewise, when the tops, wedges, and tips of structured gelshapes of FIGS. 15a-15 k are combined with a GFGC 5 (in theconfiguration shown in FIGS. 4o-4 t, 5 d, 5 e and 12 c) which isdesigned to carry all the pressure loads within the designed range ofR₂; then, the rigidities of the tops, wedges, and tips of the PRGC canhave designed gel rigidities ranges of R₁. In such cases, the tops,wedges, and tips as PRGC can be of much greater rigidities, because anyforce loading on these structured shapes will be transferred below tothe R₂ range gel rigidity GFGC 5 layer which will deform or collapse andtake the force loading first.

[0051] The progressive deformation response by the tops, wedges, andtips of the structured gel shapes of FIGS. 15a-15 k as PRGC 6 when incombination with GFGC 5 of the configurations 4 p-4 t to appliedincrease forces will produce more deformations in adjacent tops, wedges,and tips as well as in the GFGC 5 independent suspensions, therebytransferring the increased force over a greater and greater somewhatuneven loading GFGC 5 layer to produce a curved surface area of activelyengaging tops and tips while keeping the pressure within the maximumdesigned gram Bloom rigidity within gel rigidities R₂ by the overall gelbody of the GFGC 5.

[0052] The progressive deformation response of the GFGC 2 and 5 and thePRGC 1, 6, 7, 8, and 9 to an applied force by elastic bodies when suchelastic bodies are properly designed for proper respective R₁ and R₂rigidity deformations can remove plaque, as well as, save teeth and gumfrom unwanted damage.

[0053] Professor Heasman's concern that the force applied to atoothbrush could be quite light but the pressure will be much greaterbecause that force is being applied to a very small area as on the tipsof a few bristles in active contact with the teeth or gum. By properselection and use of a GFGC, the high pressure at the localized bristletips of a toothbrush impinging on the teeth and gum can be managed,gauged, arrested, prevented, controlled, mediated and/or eliminated.This problem applies to all bristles. Too much force when applied by toofew bristles, no matter their stiffness can cause damage, because thetotal applied forces are being transferred over too small a surfacearea. An elastic body with elastic recovery and of the correct rigidityis needed to “solve the too much pressure over too small a surface areaproblem.”

[0054] For a person who uses the toothbrush lightly or a “lightbrusher”, any of the plaque removing components 1, 6 7, 8, andstructures FIGS. 15a-15 k (6 being a PRGC) can be designed for notgreater than 2 mm brush deformation over a brushing surface area of 1square centimeter while engaging in brushing, then the GFGC 2 and 5 canbe selected to the desired rigidity of a comfortable 150 gram Bloom orthe weight of an orange as compared by Prof. Heasman.

[0055] In the case of a heavy brusher, any of the plaque removingcomponents 1, 6, 7, 8, and structures FIGS. 15a-15 k can be designed fornot greater than 6 mm brush deformation over a brushing surface area of3.5 square centimeter while brushing, then the GFGC 2 and 5 can beselected to the desired rigidity of a comfortable 300 gram Bloom.

[0056] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 4 mmdeformation over a surface area of 1 square centimeter, then the GFGC 2and 5 can be selected to the desired rigidity of a comfortable 150 gramBloom.

[0057] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 3 mmdeformation over a surface area of 1 square centimeter, then the GFGC 2and 5 can be selected to the desired rigidity of a comfortable 150 gramBloom.

[0058] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 1 mmdeformation over a surface area of 1 square centimeter, then the GFGC 2,and 5 can be selected to the desired rigidity of a comfortable 250 gramBloom.

[0059] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 2 mmdeformation over a surface area of 2 square centimeter, then the GFGC 2,and 5 can be selected to the desired rigidity of a comfortable 150 gramBloom.

[0060] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 3 mmdeformation over a surface area of 2 square centimeter, then the GFGC 2,and 5 can be selected to the desired rigidity of a comfortable 75 gramBloom.

[0061] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 4 mmdeformation over a surface area of 1 square centimeter, then the GFGC 2,and 5 can be selected to the desired rigidity of a comfortable 250 gramBloom.

[0062] Likewise, when any of the plaque removing components 1, 6, 7, 8,and structures FIGS. 15a-15 k can be designed for not greater than 4 mmdeformation over a surface area of 2 square centimeter, then the GFGC 2and 5 can be selected to the desired rigidity of a comfortable 150 gramBloom.

[0063]FIGS. 11a-13 c having in common hollow elastic member 10 forreceiving and holding a finger. The PRGC 6 and 9 can be made of atextured material, fibers and fabric woven or non woven loops orstructured shapes 6 suitable for plaque removal attached to the GFGC 5.The PRGC 6 in combination with the GFGC 2 and 5 can be molded onto anelectric oscillating head with or without a brush 1.

[0064] As to the physics, the forces acting on an elastic body wasformulated in to Law earlier by two other of Mr. Heasman countrymen ofHook and Young which Hook's Law states: “Ut tensio sic vis” or a changein form is proportional to the deforming force and restated by Young:that “deforming force” is “stresses.”

[0065] If a cube is subject to a uniform compression, the forces actingon each face are distributed uniformly over that area and may not beconsidered as acting at a single point. If the force is normal to thearea. then we say that the cube is subject to a pressure whose value isF/A. On the other hand, if the forces are parallel to the surfaces, thecube is subject ot a shear whose value is also given by F/A. Suchforces, distributed over area, are called “surface forces,” to becontrasted for example with the weight of an object that acts at asingle point (called a “body force”). By definition, stress is equal toforce that balances the applied force divided by the area over which theforce acts. Since the gel of the invention is much like a fluid at restand the pressure at a point in a liquid is the same in all directions orpressure is independent of direction. Wherever locally the gel body isbeing pushed, the gel pushes back everywhere over its entire surfacearea and the pressure anywhere on the gel body for a unit area is F/A.

[0066] Suitable woven and non woven fabrics, webs, fibers, or sponge asPRC in combination with GFGC such materials include woven and non wovenfabrics made from nylon, acrylic, polyester such as polyester fleece,polar fleece, spun fleece, sherpa fleece, micro fiber fleece, bouclefleece, polartec (winpro, windbloc, 100, 200,300, aleutian waffle, cord,marl, micro grid), cotton, coolmax, gore-tex fabrics (taslan, kinetic,XCR), xymid, polyurethane sponges and the like.

[0067] The gel composition suitable for use as PRGC and GFGC can be anygel meeting the requirements of rigidities R₁ and R₂, such aspolyurethane gels, silicone gels, and oil gels (SEBS, SEPS, SIS, SBS,SEEPS, SBBS, SEB/EPS, SIBS, SBEBS and the like). Combinations of lowviscosity SEBS and high viscosity SEBS gels can exhibit knotty tearresistance, while when they are un-combined, each do not. Therefore, lowviscosity SEBS, SEPS, SEEPS can be combined with high viscosity SEBS,SEEPS, and SEPS to produce better tear resistant gels. In general, highviscosity SEEPS gels perform better in knotty tear and fatigueresistance. High styrene content polymers above 35 parts by weight canperform better in knotty tear and fatigue resistance, even at lowerviscosities as compared to higher viscosity SEEPS alone. Very highviscosity SBS with high styrene content can exhibit knotty tear andfatigue resistance. While, high styrene content lower viscosity SEPS geldo not. Fully hydrogenated SEBS, SEPS, SEEPS with very low diblockcontent can exhibit greater tear properties that such polymerscontaining higher diblock content. As the diblock content increases, thetear properties becomes lower and lower. Superior tear and fatigueresistance SEEPS gel composition made from (i) 100 parts by weight ofone or a mixture of two or more of a hydrogenated styreneisoprene/butadiene block copolymer(s), wherein said (i) block copolymershave the formula poly(styrene-ethylene-ethylene-propylene-styrene); from(ii) about 300 to about 1,600 parts by weight of a plasticizing oil;said gel composition characterized by a gel rigidity of from about 20 toabout 1,800 gram Bloom; and in combination with or without (iii) aselected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, poly styrene-ethylene-styrene random copolymers producedby metallocene single site catalysts, wherein said selected copolymercan be a linear, radial, star-shaped, branched or multiarm copolymer,wherein n is greater than one; and in combination with or without (iv) aselected amount of one or more glassy component associating resinshaving softening points above about 120° C. are useful.

[0068] Another tear and fatigue resistant gel comprises: a gelcomposition of (i) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer(s);from (ii) about 300 to about 1,600 parts by weight of a plasticizingoil; said gel composition characterized by a gel rigidity of from about20 to about 800 gram Bloom; and in combination with (iii) a selectedamount of one or more block copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n), andpoly(styrene-ethylene-butylene-styrene), wherein said selected copolymercan be a linear, radial, star-shaped, branched or multiarm copolymer,wherein n is greater than one.

[0069] A further tear and fatigue resistant gel comprises: a gelcomposition of (i) 100 parts by weight of one or morepoly(styrene-ethylene-ethylene-propylene-styrene) block copolymer(s);(iii) a selected amount of one or more block copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-ethylene-propylene-styrene), andpoly(styrene-ethylene-butylene-styrene), wherein said selected copolymercan be a linear, radial, star-shaped, branched or multiarm copolymer,wherein n is greater than one; (ii) about 300 to about 1,600 parts byweight of a plasticizing oil; said gel composition characterized by agel rigidity of from about 20 to about 800 gram Bloom; and incombination with or without (iv) a selected amount of at least oneadhesion resins.

[0070] In general, the overall physical properties of amorphous gels arebetter at higher gel rigidities. The amorphous gels, however, can failcatastrophically when cut or notched while under applied forces of highdynamic and static deformations, such as extreme compression, torsion,high tension, high elongation, and the like. Additionally, thedevelopment of cracks or crazes resulting from a large number ofdeformation cycles can induce catastrophic fatigue failure of amorphousgel s, such as tears and rips between the surfaces of the amorphous geland substrates or at the interfaces of interlocking material(s) and gel.Consequently, such amorphous gels are inadequate for the most demandingapplications involving endurance at high stress and strain levels overan extended period of time.

[0071] The various types of copolymers and block copolymers employed informing the gels of the invention are of the general configurations(Y-AY)_(n) copolymers, A-Z-A, and (A-Z)_(n) block copolymers, whereinthe subscript n is a number of two or greater. In the case of multiarmblock copolymers where n is 2, the block copolymer denoted by (A-Z)_(n)is A-Z-A. It is understood that the coupling agent is ignored for sakeof simplicity in the description of the (A-Z)_(n) block copolymers. Thesegment (A) comprises a glassy amorphous polymer end block segment whichcan be polystyrene, poly(alpha-methylstyrene), poly(o-methylstyrene),poly(m-methylstryene), poly(p-methylstyrene) and the like, preferably,polystyrene.

[0072] The segment (Y) of copolymers (Y-AY)_(n) comprises crystallizablepoly(ethylene) (simply denoted by “-E-” or (E)). In the case ofcopolymers (A-Y)_(n), (Y) when next to (A) may be substantiallynon-crystalline or amorphous ethylene segments. For example acrystallizable copolymer (Y-AY)_(n) may be represented by: . . .-E-E-E-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE-E-E-E-E-E-E-SE-. . . . Where Y is along run of polyethylene or a non-crystalline copolymer (AY-AY)_(n): . .. -E-SE-SE-E-SE-E-SE-E-SE-E-E-SE-SE-E-SE- . . . where Y is anon-crystalline run of ethylene.

[0073] Other substantially random copolymers suitable for forminginvention gels of the invention include (Y-A-Y′) where Y is acrystallizable run of ethylene and Y′ can be propylene,4methyl-1-pentene, hexene-1, octene-1, and norborene. A can be styrene,vinyl toluene, alpha-methylstyrene, t-butylstyrene, chlorostyrene,including isomers and the like. Examples are: poly(ethylene-styrene)(ES), poly(ethylene-styrene-propylene) (ESP),poly(ethylene-styrene-4methyl-1-pentene) (ES4M 1P),poly(ethylene-styrene-hexend-1) (ESH1), poly(ethylene-styrene-octene-1)(ESO1), and poly(ethylene-styrene-norborene) (ESN),poly(ethylene-alpha-methylstyrene-propylene),poly(ethylene-alpha-methylstyrene-4-methyl-1-pentene),poly(ethylene-alpha-methylstyrene-hexend-1),poly(ethylene-alpha-methylstyrene-octene-1), andpoly(ethylene-alpha-methylstyrene-norborene) and the like.

[0074] The end block segment (A) comprises a glassy amorphous polymerend block segment which can be polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene) andthe like, preferably, polystyrene. The segment (Y) of random copolymersA-Y comprises crystallizable poly(ethylene) (simply denoted by “-E-” or(E)). In the case of random copolymers A-Y, (Y) may be substantiallynon-crystalline or amorphous ethylene segments. The midblocks (Z)comprises one or more midblocks of crystallizable poly(ethylene) (simplydenoted by “-E- or (E)”) with or without one or more amorphous midblocksof poly(butylene), poly(ethylene-butylene), poly(ethylene-propylene) orcombination thereof (the amorphous midblocks are denoted by “-B- or(B)”, “-EB- or (EB)”, and “-EP- or (EP)” respectively or simply denotedby “-W- or (W)” when referring to one or more of the amorphous midblocksas a group) The A and Z, and A and Y portions are incompatible and forma two or more-phase system consisting of sub-micron amorphous glassydomains (A) interconnected by (Z) or (Y) chains. The glassy domainsserve to crosslink and reinforce the structure. The number averagemolecular weight (Mn) of the random copolymers is preferably greaterthan 1,000, advantageously from about 5,000 to about 1,100,000, moreadvantageously from abut 8,000 to about 700,000. Examples are:

[0075] The method of making Y-A-Y and Y-A-Y′ random copolymers bymetallocene single site catalysts are described in U.S. Pat. Nos.5,871,201, 5,470,993, 5,055,438, 5,057,475, 5,096,867, 5,064,802,5,132,380. 5,189,192, 5,321,106, 5,347,024, 5,350,723, 5,374,696,5,399,635, and 5,556,928, 5,244,996, application EP-A-0416815,EP-A-514828, EP-A-520732, WO 94/00500 all of which disclosure areincorporated herein by reference.

[0076] The linear block copolymers are characterized as having aBrookfield Viscosity value at 5 weight percent solids solution intoluene at 30° C. of from less than about 40 cps to about 60 cps andhigher, advantageously from about 40 cps to about 160 cps and higher,more advantageously from about 50 cps to about 180 cps and higher, stillmore advantageously from about 70 cps to about 210 cps and higher, andeven more advantageously from about 90 cps to about 380 cps and higher.

[0077] The branched, star-shaped (radial), or multiarm block copolymersare characterized as having a Brookfield Viscosity value at 5 weightpercent solids solution in toluene at 30° C. of from about 80 cps toabout 380 cps and higher, advantageously from about 150 cps to about 260cps and higher, more advantageously from about 200 cps to about 580 cpsand higher, and still more advantageously from about 100 cps to about800 cps and higher.

[0078] The poly(ethylene/styrene) copolymers, type S series has morethan 50 wt % styrene and is glassy at short times and rubbery at longtimes and exhibits ambient Tg, melt density of about higher than 0.952to about 0.929 and less, typical Mw=about less than 150,000 to 350,000and higher. The type M series has more than 50 wt % styrene is amorphousrubber and exhibits very low modulus, high elasticity, low Tg of fromgreater than 10° C. to less than −50,° C., melt Index of from higherthan 5 to less than about 0.1, melt density of higher than 0.93 to 9.0and less, typical Mw=about less than 200,000 to 300,000 and higher. Thetype E series contains up to 50 wt % styrene is semi-crystalline rubberand exhibits low Tg of from greater than 0° C. to about less than −70,low modulus semi-crystalline, good compression set, Melt Index of fromabout higher than 2 to less than 0.03, melt density of about higher than0.90 to 0.805 and less, Mw=about less than 250,000 to 350,000 andhigher. The E series random copolymers can be blended with the type Mand type S series copolymers (having high glassy components) and one ormore of the i, ii, iii, iv, v, vii and viii copolymers, plasticizers toform crystallizable polymer invention gels of the invention.

[0079] This physical elastomeric network structure can be reversible,and heating the polymer above the softening point of the glassy domainstemporarily disrupt the structure, which can be restored by lowering thetemperature. During mixing and heating in the presence of compatibleplasticizers, the glassy domains (A) unlock due to both heating andsolvation and the molecules are free to move when shear is applied. Thedisruption and ordering of the glassy domains can be viewed as aunlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (Z) or (A) and (Y) phases (mesophases) can take the form of spheres,cylinders, lamellae, or bicontinous structures. The scale of separationof the phases are typically of the order of hundreds of angstroms,depending upon molecular weights (i.e. Radii of gyration) of theminority-component segments. The sub-micron glassy domains whichprovides the physical interlocking are too small to see with the humaneye, too small to see using the highest power optical microscope andonly adequately enough to see using the electron microscope. At suchsmall domain scales, when the gel is in the molten state while heatedand brought into contact to be formed with any substrate and allowed tocool, the glassy domains of the gel become interlocked with the surfaceof the substrate. At sufficiently high enough temperatures, with orwithout the aid of other glassy resins (such as polystyrene homopolymersand the like), the glassy domains of the copolymers forming the gelsfusses and interlocks with even a visibly smooth substrate surface suchas glass. The disruption of the sub-micron domains due to heating abovethe softening point forces the glassy domains to open up, unlocking thenetwork structure and flow. Upon cooling below the softening point, theglassy polymers reforms together into sub-micron domains, locking into anetwork structure once again, resisting flow. It is this unlocking andlocking of the network structure on the sub-micron scale with thesurfaces of various materials which allows the gel to form interlockingwith other materials.

[0080] A useful analogy is to consider the melting and freezing of awater saturated substrate, for example, foam, cloth, fabric, paper,fibers, plastic, concrete, and the like. When the water is frozen, theice is to a great extent interlocked with the substrate and upon heatingthe water is able to flow. Furthermore, the interlocking of the ice withthe various substrates on close examination involves interconnecting icein, around, and about the substrates thereby interlocking the ice withthe substrates. A further analogy, but still useful is a plant or weedwell established in soil, the fine roots of the plant spreads out andinterconnects and forms a physical interlocking of the soil with theplant roots which in many instances is not possible to pull out theplant or weed from the ground without removing the surrounding soilalso.

[0081] Likewise, because the glassy domains are typically about 200Angstroms in diameter, the physical interlocking involve domains smallenough to fit into and lock with the smallest surface irregularities, aswell as, flow into and flow through the smallest size openings of aporous substrate. Once the gel comes into contacts with the surfaceirregularities or penetrates the substrate and solidifies, it becomesdifficult or impossible to separate it from the substrate without pullbecause of the physical interlocking. When pulling the gel off asubstrate, most often the physically interlocked gel remains on thesubstrate, but not always depending on the substrate and the adhesiveforces. Even a surface which may appear perfectly smooth to the eye, itis often not the case. Examination by microscopy, especially electronmicroscopy, will show serious irregularities. Such irregularities can bethe source of physical interlocking with the gel. The locking of thegrassy domains allows the gel to (stay-put) not easily moved or pull outfrom the substrate.

[0082] Such interlocking with many different materials produce gelshaving many uses including forming useful composites, such as PRGC andGFGC of the invention. The gel compositions is denoted as “G” can bephysically interlocked or formed in contact with a selected materialdenoted as “M” denoted for simplicity by their combinations G_(n)G_(n),G_(n)M_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n),G_(n)G_(n)M_(n), M_(n)M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n) G_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), and the like or any of theirpermutations of one or more Gn with Mn and the like, wherein when n is asubscript of M, n is the same or different selected from the groupconsisting of foam, plastic, fabric, metal, concrete, wood, glass,ceramics, synthetic resin, synthetic fibers or refractory materials andthe like; wherein when n is a subscript of G, n denotes the same or adifferent gel rigidity of from about 20 to about 800 gram Bloom). Thegel compositions and articles of the composites can be formed from I,II, and III components described above.

[0083] Sandwiches of invention gel-material (i.e., inventiongel-material-invention gel or material-invention gel-material, etc.) areuseful as dental floss, shock absorbers, acoustical isolators, vibrationdampers, vibration isolators, and wrappers. For example the vibrationisolators can be use under research microscopes, office equipment,tables, and the like to remove background vibrations. The tearresistance nature of the invention gels are superior in performance toamorphous block copolymer gels which are much less resistance to crackpropagation caused by long term continue dynamic loadings.

[0084] The high tear resistant soft invention gels are advantageouslysuitable for a safer impact deployable air bag cushions, other usesinclude: toys; games; novelty, or souvenir items; elastomeric lenses,light conducing articles, optical fiber connectors; athletic and sportsequipment and articles; medical equipment and articles including dermause and for the examination of or use in normal or natural bodyorifices, health care articles; artist materials and models, specialeffects; articles designed for individual personal care, includingoccupational therapy, psychiatric, orthopedic, podiatric, prosthetic,orthodontic and dental care; apparel or other items for wear by and onindividuals including insulating gels of the cold weather wear such asboots, face mask, gloves, full body wear, and the like have as anessential, direct contact with the skin of the body capable ofsubstantially preventing, controlling or selectively facilitating theproduction of moisture from selected parts of the skin of the body suchas the forehead, neck, foot, underarm, etc.; cushions, bedding, pillows,paddings and bandages for comfort or to prevent personal injury topersons or animals; house wares and luggage; articles useful intelecommunication, utility, industrial and food processing, PRGC, GFGC,and the like as further described herein.

[0085] Cushion in the form of crumpets can be formed by utilizing theaeration method described in U.S. Pat. No. 4,240,905 (which isincorporated herein by reference) instead of high solids, inert gas isintroduced through a multi holed mold base at positive pressuredepending on the working viscosity of the molten invention gel and gelblends without repeatedly shearing the rising injected gas streamsthereby forming cushions having natural structures similar to crumpetsupon cooling in the mold. Also long metal netting needles of any desireddiameter are projected through multi holed mold base, top and side wallsin various directions creating a multi directional hollowed network whenmolten gel is injected, poured, or transferred into the enclosed moldunder positive pressure and allowed to cool. The needles are easilyremoved one by one or altogether at once leaving the described multichanneled gel cushion. Likewise the inert gas injected into a gel bodywhile in the molten state can be sheared at desired time intervals so asto provide hollowed cushions with any desired void shaped volumes. Acrumpet looks like a shaped volume with a smooth bottom and sidecontaining many small holes a few millimeter in diameter which holes areextended from near the bottom to the top of the crumpet.

[0086] Health care devices such as face masks for treatment of sleepdisorder require non-tacky invention gels of the invention. Theinvention gel forming a gel overlap portion on the face cup at its edgeconforming to the face and serve to provide comfort and maintain partialair or oxygen pressure when worn on the face during sleep. Other healthcase uses include pads in contact with the body use in wound healing andburn treatment, the gel can also be use as a needle protector sheath,tubing for medical fluid sets, as male and female connectors, sealingcaps, a pad use for compression at needle injection site to preventinjury to the blood vessel.

[0087] When utilized as a needle protector sheath, a invention gelcomposition made from SEEPS in combination with or without otherpolymers, and copolymers is of advantage because of its higher rupturetear resistance properties. SEBS and SEPS in combination with lowviscosity SEBS can also be use to advantage, but with a noticeabledecrease in rupture resistance. The needle can be secured by forcing thesharp point into the gel volume of a desired shaped gel body. In doingso, automatically the sharped needle is secured safely within the gelbody preventing the sharp needle from accidentally injuring the healthworker or anyone else in contact with the needle device. Moreover, theliquid be it medication or body fluids are also securely and safelycontained in the gel body. The gel automatically plug the tip of thesharp needle so as to prevent any liquid from leaving the tip of theneedle. Moreover the gel body containing the needle can be in safecontact when accidentally placed on or near a body while work is beingperformed. The holding power or force holding the sharp needle can beadjusted by formulating the gel to any desired rigidity. The greater therigidity, the greater the holding force of the gel on the needle. Suchneedle can be inserted into a gel body at any desired angle from lessthan 1° to less than 180° without loss of holding force on the needle.The gel needle protector sheath can be any desired size. A large gripsize is useful so as not to readily misguide the needle into the gelbody. A small size is useful so as not to be too bulky for storage. Therequirement of the gel body as a needle sheath protector is that whendrop from a height of 3 feet or 1 meter, the needle should not be ableto penetrate through the gel body adjacent to the tip, therebymaintaining integrity of the seal and afford adequate protection tomedical workers. The other requirement is that the gel body should havesufficient holding force gripping the needle while it rest within thegel body that it does not easily slip out accidentally. Such force canbe selected to be greater than the weight of the needle and attachedinstrument the needle is physically attached. A rigidity in gram Bloomof greater than 100 gram is desirable for gripping the needle and holdit in place. Higher rigidity are of advantage, such as 100, 200, 300,400, 500, 600, 800,1000, 2000, and higher.

[0088] Connectors, such as luer lock connectors, friction fitconnectors, or other types of connectors for blood tubing especiallyuseful for dialysis including use in connecting blood sets, hemodialysistube sets, bubble trap inlet and outlet tubing, closures, caps and thelike can be contaminated easily. A not so general information is thatmedical works do not take the time to decontaminate or safe guardconnectors. The connectors are plug in and unplugged when needed andalmost no one see to the cleanliness of the connectors before plug theconnectors together, there is just no time for it. The need to plug andunplug connectors in the health service environment is that theconnectors come in two types: male and female use to make everyconnection and the male and female parts come separately because at thetime of manufacture they are made separately. The invention gel of highrigidity made from gel compositions of 250 to 400 parts by weight ofblock copolymers are useful for making tubing and tubing connectors.Surprisingly, if a male mold is use to made the male connector part, themale connector part can be allowed to cool in the mold and the same moldholding the male connector part can than be injected with additional gelof suitable rigidity to form the opposite female part. When the moldcontaining the male and female connector parts are cooled sufficient,both male and female connectors are demolded at the same time andpackaged without contamination. The connectors can be molded with thesame gel material tubing or if molded separately, the connectors neednot be taken apart until needed. The novelty is that when the inventiongels are sufficiently cooled to above room temperature, a second andfollowed by a third and the like molten gel can be in contact with thecooled gel and when both have cooled sufficiently the two parts willcome apart. They do not bond in any way. Therefore a gel articlenegative can receive molten gel utilizing the negative gel to form apositive. This reduces the cost of making two molds, a positive and anegative. Only one is necessary to make both parts.

[0089] Tacky gels because of its tactile feel are undesirable for suchapplications while other application require gel adhesion to the skinand selected substrates. Gels are inherently sticky or tacky to thetouch, especially soft thermoplastic elastomer oil gels which canexhibit extreme tackiness when compounded with high viscosity oils. Thetackiness can be reduced, masked or removed by powdering the gel'soutside surface or by incorporating additives which will eventuallymigrate to the gel's outer surface. Such additives being effective onlyat the gel's surface. The migration of additives from within the bulkgel to the gel's surface is generally due to gradients of pressure ortemperature, weak, moderate, or strong molecular dipo/dipo ordipo/non-dipo interactions within the gel. The additives, however, cancause the gels to be translucent or opaque throughout their volume asfound in my U.S. Pat. No. 5,760,117 which describes surface activatednon-tacky gels. Once the additives are transported from within the gelto the surface forming an “additive layer”. Although the additive layercan reduced tackiness or no tack at the gel's surface, the additivelayer can themselves impart their own tactical character. For example,stearic acid exhibits a low melting point and tends to be somewhatgreasy at ambient or above ambient temperatures. Once the gel is damagedor cut, the tackiness of the freshly cut area is exposed.

[0090] The gelatinous elastomer compositions of the present inventioncan be made firm or soft, tacky, adherent or non-tacky to the touch. The“non-tacky to the touch” gelatinous elastomer compositions of theinvention is not based on additives which bloom to the surface to reducetack. For simplicity, the gelatinous elastomer compositions of theinvention (which are highly tear resistant and rupture resistant and canbe made tacky, adherent, non-tacky to the touch and opticallytransparent or clear) will be referred to herein as “invention gel(s)”which includes “tear resistant gels”, “rupture resistant gels”,“non-tacky gels”, “no tack gels”, “optical gels”, “tacky gels”,“adherent gels”, and the like when referring to certain propertyattributes of the various gels or more simply refer to as “the gel(s)”or “said gel(s)”. Gels of the invention are described herein below forevery use.

[0091] As described herein, the conventional term “major” means greaterthan 50 parts by weight and higher (e.g. 5.01, 50.2, 50.3, 50.4, 50.5, .. . 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67,68, 69, . . . 580 and higher based on 100 part by weight of (I)copolymers) and the term “minor” means 49.99 parts by weight and lower(e.g. 49, 48, 47, 46, 45, 44, 43, 42, 41 , 40, 39, 38, 37, 36, 35, 34,33, 32, 21, . . . 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7 . . .0.09 and the like) based on 100 parts by weight of the base (I) blockcopolymer(s).

[0092] It should be understood that although the conventional term“parts by weight” is used, the term “parts by weight” is ordinarily usedin rubber tire and rubber goods and other formulations. This terms ormethod of formulation is especially useful and easy to keep track ofchanges made in formulation work as changes are often needed to arriveat an optimum formulation to improve one property or another. Each ofthe components which go into a formulation are weight out, except forthe “rubber” or base “polymer” which is kept at a constant “100 parts byweight”. A simple notation is “hpr” or “hundred parts of rubber” or“pphr” which spells out to read “parts per hundred of rubber”.

[0093] Any units of weight measure can be use, depending on theavailable scale used (grams, pounds, oz, etc.). Parts by weight isuseful, because not every one on uses the same units of measure. One canconvert from “100 parts by weight of rubber” to weight %. For example,“parts by weight of (b)” and “parts by weight of (c)” are based withrespect to 100 parts by weight of component “(a)”:

[0094] A formulation based on parts by weight can be calculated asfollows: Add to 100 parts by weight of elastomer “A”, 300 parts byweight oil “B”, 49 parts by weight resin “C”. This formulation has atotal weight of “449” which can be in grams, pounds, tons, whatever unitof weight measurement used. In order to convert this formulation into %,we simply divide each of the components by 449”resulting:%A=(100/449)×100=(0.2227271)×100=22.27271%=elastomer,%B=(300/449)×100=(0.6681514)×100=66.81514%=oil,%C=(49/449)×100=(0.1091314)×100=10.91314%=resin, and a Total %=99.99999%or 100%

[0095] If we performed the measurements in grams, than 100 grams offormulation “ABC” would simply contain 22.27271 grams elastomer,66.81514 grams of oil, and 10.91314 grams of resin. Consistent with thishundred year old methodology are the terms minor and major with respectto “100 parts by weight of rubber”. An amount less than about 50 partsby weight with respect to “100 parts by weight of rubber” would beconsidered “minor amount.” An amount greater than 50 parts by weightwith respect to “100 parts by weight of rubber” would be considered“major amount.”

[0096] Gels are inherently sticky or tacky to the touch, especially softthermoplastic elastomer oil gels which can exhibit extreme tackinesswhen compounded with high viscosity oils. The tackiness can be reduced,masked or removed by powdering the gel's outside surface or byincorporating additives which will eventually migrate to the gel's outersurface. Such additives being effective only at the gel's surface. Themigration of additives from within the bulk gel to the gel's surface isgenerally due to gradients of pressure or temperature, weak, moderate,or strong molecular dipo/dipo or dipo/non-dipo interactions within thegel. The additives, however, can cause the gels to be translucent oropaque throughout their volume as found in my U.S. Pat. No. 5,760,117which describes surface activated non-tacky gels. Once the additives aretransported from within the gel to the surface forming an “additivelayer”. Although the additive layer can reduced tackiness or no tack atthe gel's surface, the additive layer can themselves impart their owntactical character. For example, stearic acid exhibits a low meltingpoint and tends to be somewhat greasy at ambient or above ambienttemperatures. Once the gel is damaged or cut, the tackiness of thefreshly cut area is exposed.

[0097] Not only can the invention gels be made tacky and adherent to anydegree desired or non-tacky to the touch, the gels are naturallytransparent, and optically clear suitable for optical use. The gels arestrong, elastic, highly tear resistant, and rupture resistant. Theinvention gels can be formed into any shape for the intended use such assolid shapes for use as articles of manufacture, thin and thick sheets,strands, strings, ropes, fibers, fine silk like filaments can be appliedin its molten state onto various substrates.

[0098] The invention gels of the invention can be formed into gelstrands, gel bands, gel tapes, gel sheets, and other articles ofmanufacture in combination with or without other substrates or materialssuch as natural or synthetic fibers, multifibers, fabrics, films and thelike. Moreover, because of their improved tear resistance and resistanceto fatigue, the invention gels exhibit versatility as balloons formedical uses, such as balloon for valvuloplasty of the mitral valve,gastrointestinal balloon dilator, esophageal balloon dilator, dilatingballoon catheter use in coronary angiogram and the like. Since theinvention gels are more tear resistant, they are especially useful formaking condoms, toy balloons, and surgical and examination gloves. Astoy balloons, the invention gels are safer because it will not ruptureor explode when punctured as would latex balloons which often timescause injures or death to children by choking from pieces of latexrubber. The invention gels are advantageously useful for making gloves,thin gloves for surgery and examination and thicker gloves for vibrationdamping which prevents damage to blood capillaries in the fingers andhand caused by handling strong shock and vibrating equipment. Variousother gel articles can be made from the advantageously tear resistantgels and gel s of the inventions include gel suction sockets, suspensionbelts.

[0099] The invention gels are also useful for forming orthotics andprosthetic articles such as for lower extremity prosthesis describedbelow.

[0100] Advantageously, the invention gels of the invention are non-tackyrequires no additive. Its non-tackiness are an inherent property of thecrystallinity, glassy A components, and selected low viscosityplasticizers forming the invention gels of the invention. Such inventiongels, however, must met the following criteria: (a) the invention gelsare made from A-Z-A, (A-Z)_(n), (A-Y)_(n), (Y-AY)_(n) and (Y-AY′)_(n)copolymers: crystallizable block copolymers and crystallizablepoly(ethylene-styrene) substantially random copolymers of the type S, M,and E series (for example SEEPS, S-E-EB-S, S-EB45-EP-S, S-E-EB25-S,S-E-EP-E-S, S-EP-E-S, S-EP-E-EP-S, E-S-E, (E-S)_(n), (E-S-E)_(n), (ESP),(ES4M1P), (ESH1), (ESO1), (ESN) and(S-E-EP)_(n), crystallizable S-EB-Swith elastomeric crystallizable block:glassy block ratios of 89:11,88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21,78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, and 70:30) andthe like; (b)the invention gels can be made from copolymers havingcrystallizable poly(ethylene) segments exhibit crystallization exothermvalues of about less than 10° C., 20° C., 25° C., 26° C., 27° C., 28°C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37°C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46°C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C.,55°C., 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C.,64° C, 65° C., 66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C.and higher; and (C)the invention gels can be made from copolymers havingglassy A to Y or glassy A to Z ratios of at least 37:63, higher ratiosare also of advantage, such as: 38:62, 39:61, 40:60, 41:59, 42:58,43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49, 52:48,53:47, 54:46, 55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 61:39, 62:38,63:37, 64:36, 65:35, 66:34; or by the addition of (d) sufficient amountsof glassy homopolymers or glass associated phase resins so thatcondition (c) is met.

[0101] Not to be bound by theory, the combination of sufficient amountsof crystallinity and sufficient amounts glassy A components of thecopolymers in combination with low viscosity plasticizers impartsnon-tackiness to the invention gels of the invention. It is thereforecontemplated that the same effect can be achieved by blending highlycrystallizable and highly glassy copolymers (Dow S, M, & E SeriesE-S-E), with less crystallizable and less glassy copolymers such asamorphous SEPS, SEBS, and amorphous S-EB-EP-S and other amorphouscopolymers provided the amorphous copolymers are in minor amounts andthere is substantial crystallinity and sufficient over all glassy Acomponents to meet conditions (c).

[0102] The glassy homopolymers of (d) are advantageously selected fromone or more homopolymers of: polystyrene, poly(alpha-methylstyrene),poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene), andpoly(dimethylphenylene oxide). The average molecular weight of theglassy homopolymers advantageously can range from and in between about2,500 to about 90,000, typical about 3,000; 4,000; 5,000; 6,000; 7,000;8,000; 9,000; 10,000; 11,000; 12,000, 13,000; 14,000; 15,000; 16,000;17,000; 18,000; 19,000; 20,000; 30,000; 40,000; 50,000; 60,000; 70,000;80,000; 90,000 and the like. Example of various molecular weights ofcommercially available polystyrene: Aldrich Nos.: 32,771-9 (2,500 Mw),32,772-7 (4,000 Mw), 37,951-4 (13,000 Mw), 32-774-3 (20,000 Mw),32,775-1 (35,000 Mw), 33,034-5 (50,000 Mw), 32,777-8 (90,000 Mw);poly(alpha-methylstyrene) #41,794-7 (1,300 Mw), 19,184-1 (4,000 Mw);poly(4-methylstyrene) #18,227-3 (72,000 Mw), Endex 155, 160, Kristalex120, 140 from Hercules Chemical, GE: Blendex HPP820, HPP822, HPP823, andthe like. Various glassy phase associating resins having softeningpoints above about 120° C. can also serve to increase the glassy phaseof the Invention gels of the invention and met the non-tackinesscriteria, these include: Hydrogenated aromatic resins (Regalrez 1126,1128, 1139, 3102, 5095, and 6108), hydrogenated mixed aromatic resins(Regalite R125), and other aromatic resin (Picco 5130, 5140, 9140, CumarLX509, Cumar 130, Lx-1035) and the like.

[0103] On the other hand, the molten gelatinous elastomer compositionwill adhere sufficiently to certain plastics (e.g. acrylic, ethylenecopolymers, nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F.). Commercialresins which can aid in adhesion to materials (plastics, glass, andmetals) may be added in minor amounts to the gelatinous elastomercomposition, these resins include: Super Sta-tac, Nevtac, Piccotac,Escorez, Wingtack, Hercotac, Betaprene, Zonarez, Nirez, Piccolyte,Sylvatac, Foral, Pentalyn, Arkon P, Regalrez, Cumar LX, Picco 6000,Nevchem, Piccotex, Kristalex, Piccolastic, LX-1035, and the like.

[0104] The commercial resins which can aid in adhesion to materials(plastics, glass, and metals) may be added in minor amounts to thegelatinous elastomer composition, these resins include: polymerizedmixed olefins (Super Sta-tac, Betaprene Nevtac, Escorez, Hercotac,Wingtack, Piccotac), polyterpene (Zonarez, Nirez, Piccolyte, Sylvatac),glycerol ester of rosin (Foral), pentaerythritol ester of rosin(Pentalyn), saturated alicyclic hydrocarbon (Arkon P), coumarone indene(Cumar LX), hydrocarbon (Picco 6000, Regalrez), mixed olefin (Wingtack),alkylated aromatic hydrocarbon (Nevchem), Polyalphamethylstyrene/vinyltoluene copolymer (Piccotex), polystyrene (Kristalex, Piccolastic),special resin (LX-1035), and the like. More earlier, I had alsodisclosed the use of liquid tackifiers in high viscosity SEBS gels.

[0105] The incorporation of such adhesion resins is to provide strongand dimensional stable adherent invention gels, gel s, and gel articles.Typically such adherent invention gels can be characterized as adhesivegels, soft adhesives or adhesive sealants. Strong and tear resistantadherent invention gels may be formed with various combinations ofsubstrates or adhere (attach, cling, fasten, hold, stick) to substratesto form adherent invention gel/substrate articles and s.

[0106] Various substrate and adherent invention gel combinations whichcan be utilized to form adherent invention gel articles include:G_(n)G_(n), G_(n)M_(n), G_(n)M_(n)G_(n), M_(n)G_(n)M_(n, M) _(n)G_(n)Gn,G_(n)G_(n)M_(n), M_(n)M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n) G_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), or any permutations of said combination,where G=gel and M=material. The subscript 1, 2, 3, 4, etc., aredifferent and is represented by n which is a positive number, when n isa subscript of M, n may be the same or different material and when n isa subscript of G, n can be the same or different rigidity adherentinvention gel or the same or different adherent invention gel materialcomposition. The material (M) suitable for forming articles with thegelatinous elastomer compositions can include foam, plastic, fabric,metal, concrete, wood, wire screen, refractory material, glass,synthetic resin, synthetic fibers, and the like. Sandwiches of adherentinvention gel/material (i.e. adherent invention gel-material-adherentinvention gel or material-adherent invention gel-material, etc.) areideal for use as shock absorbers, acoustical isolators, vibrationdampers, vibration isolators, and wrappers. For example the vibrationisolators can be use under research microscopes, office equipment,tables, and the like to remove background vibrations.

[0107] Various useful adhesion resins of one or more types can beincorporated in minor amounts into the adherent invention gel. Theseinclude: polymerized mixed olefins, polyterpene, glycerol ester ofrosin, pentaerythritol ester of rosin, saturated alicyclic hydrocarbon,coumarone indene, hydrocarbon, mixed olefin, alkylated aromatichydrocarbon, Polyalphamethylstyrene/vinyl toluene copolymer,polystyrene, special resin, and the like.

[0108] The adherent invention gel compositions of the invention can becasted unto various substrates, such as foam, plastic, fabric, metal,concrete, wood, wire screen, refractory material, glass, syntheticresin, synthetic fibers, and the like, or the adherent invention gelsformed and then can be adhere (attach, cling, fasten, hold, stick) tothe desired substrates to form various G_(n)G_(n), G_(n)M_(n),G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), G_(n)G_(n)M_(n),M_(n)M_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n), M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)M_(n)G_(n), G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n), G_(n)M_(n)G_(n)G_(n),G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n), or any permutations of said combinations for uses requiring temporary peel and re-use as well as permanentlong-life use as needed. Adhesion to substrates is most desirable whenit is necessary to apply the adherent invention gels to substrates inthe absence of heat or on to a low temperature melting point substratefor later peel off after use, such as for sound damping of a adherentinvention gel applied to a first surface and later removed for use on asecond surface. The low melting substrate materials which can not beexposed to the high heat of the molten adherent invention gels, such aslow melting metals, low melting plastics (polyethylene, PVC, PVE, PVA,and the like) can only be formed by applying the adherent invention gelsto the temperature sensitive substrates. Other low melting plasticsinclude: polyolefins such as polyethylene, polyethylene copolymers,ethylene alpha-olefin resin, ultra low density ethylene-octene-1copolymers, copolymers of ethylene and hexene, polypropylene, and etc.Other cold applied adherent invention gels to teflon type polymers: TFE,PTFE, PEA, FEP, etc., polysiloxane as substrates are achieved using theadherent invention gels of the invention.

[0109] Likewise, adherent invention gel substrate s can be both formedby casting hot onto a substrate and then after cooling adhering theopposite side of the adherent invention gel to a substrate having a lowmelting point. The adherent invention gel is most essential when it isnot possible to introduce heat in an heat sensitive or explosiveenvironment or in outer space. The use of solid or liquid resinspromotes adherent invention gel adhesion to various substrates bothwhile the adherent invention gel is applied hot or at room temperatureor below or even under water. The adherent invention gels can be appliedwithout heating to paper, foam, plastic, fabric, metal, concrete, wood,wire screen, refractory material, glass, synthetic resin, syntheticfibers, and the like.

[0110] The adhesion properties of the gels can be determined bymeasuring comparable rolling ball tack distance “D” in cm using astandard diameter “d” in mm stainless steel ball rolling off an inclinedof height “H” in cm and determining the average force required toperform 180° peel of a heat formed GIMI one inch width sample applied atroom temperature to a substrate M₂ to form the M₁G₁M₂ The peel at aselected standard rate crosshead separation speed of 25 cm/minute atroom temperature is initiated at the G₁M₂ interface of the M₁G₁M₂, wherethe substrate M₂ can be any of the substrates mentioned and M1preferably a flexible fabric.

[0111] Advantageously, glassy phase associating homopolymers such aspolystyrene and aromatic resins having low molecular weights of fromabout 2,500 to about 90,000 can be blended with the triblock copolymersof the invention in large amounts with or without the addition ofplasticizer to provide a copolymer-resin alloy of high impact strengths.More advantageously, when blended with multiblock copolymers andsubstantially random copolymers the impact strengths can be even higher.The impact strength of blends of from about 150 to about 1,500 parts byweight glass phase associating polymer and resins to 100 parts by weightof one or more multiblock copolymers can provide impact strengthapproaching those of soft metals. At the higher loadings, the impactstrength approaches that of polycarbonates of about 12 ft-lb/in notchand higher.

[0112] The improvements of the invention gels of the invention isexceptional, the invention gels are non tacky to the touch and can bequantified using a simple test by taking a freshly cut Invention gelprobe of a selected gel rigidity made from the invention gels of theinvention. The invention gel probe is a substantially uniformcylindrical shape of length “L” of about 3.0 cm formed components(1)-(3) of the invention gels of the invention in a 16×150 mm test tube.The invention gel probe so formed has a 16 mm diameter hemispherical tipwhich (not unlike the shape of a human finger tip) is brought intoperpendicular contact about substantially the center of the top cover ofa new, untouched polystyrene reference surface (for example the topcover surface of a sterile polystyrene petri dish) having a diameter of100 mm and a weight of 7.6 gram resting on its thin circular edge (whichminimizes the vacuum or partial pressure effects of one flat surface incontact with another flat surface) on the flat surface of a scale whichscale is tared to zero. The probe's hemispherical tip is place incontact with the center of the top of the petri dish cover surface andallowed to remain in contact by the weight of the gel probe while heldin the upright position and then lifted up. Observation is maderegarding the probe's tackiness with respect to the clean referencepolystyrene surface. For purpose of the foregoing reference tack test,tackiness level 0 means the polystyrene dish cover is not lifted fromthe scale by the probe and the scale shows substantially an equalpositive weight and negative weight swings before settling again back tozero with the swing indicated in (negative) grams being less than 1.0gram. A tackiness level of one 1, means a negative swing of greater than1.0 gram but less than 2.0 gram, tackiness level 2, means a negativeswing of greater than 2 gram but less than 3 gram, tackiness level 3,means a negative swing of greater than 3 gram but less than 4 gram,before settling back to the zero tared position or reading. Likewise,when the negative weight swing of the scale is greater than the weightof the dish (i.e., for the example referred above, greater than 7.6gram), then the scale should correctly read −7.6 gram which indicatesthe dish has completely been lifted off the surface of the scale. Suchan event would demonstrate the tackiness of a gel probe havingsufficient tack on the probe surface. The invention gels of theinvention fails to lift off the polystyrene reference from the surfaceof the scale when subject to the foregoing reference tack test.Advantageously, the invention gels of the invention can register atackiness level of less than 5, more advantageously, less than 3, stillmore advantageously, less than 2, and still more advantageously lessthan 1. The non-tackiness of the invention gels of the invention canadvantageously range from less than 6 to less than 0.5 grams, typicaltack levels can be less than or in between about 0.2, 0.3, 0.4, 0.5,0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, 2.2, 2.3, 2.5, 2.8, 3.0, 3.5, 4.0, 4.5, 5.0 grams and thelike. Whereas probes of gels made from amorphous gels such as SEPS,SEBS, S-EP-EB-S, and the like with copolymer styrene to rubber ratio ofless than 37:63 and plasticizer of higher than 30 cSt 40° C. are foundto lift the polystyrene reference from the surface of the scale. Forpurposes of indicating tack, the method above can provide gel tack levelreadings of 1, 2, 3, 4, 5, 6, and 7 grams. More accurate and sensitivereadings can be made using electronic scales of tack levels of less than1 gram. By this simple method tack levels (of a gel probe on apolystyrene reference surface) can be measure in terms of gram weightdisplacement of a scale initially tared to zero. For purpose of thepresent invention the method of using a polystyrene reference surfacehaving a weight of 7.6 grams in contact and being lifted by thetackiness of a cylindrical gel probe having a 16 mm diameterhemispherical tip is used to determine the tackiness of the inventiongels of the invention. The level of tack being measured in gram Tack at23° C.

[0113] The improvements of other properties of the invention gels overamorphous gels are many, these include: improved damage tolerance,improved crack propagation resistance, improved tear resistance,improved resistance to fatigue, etc. Such invention gels areadvantageous for end-use involving repeated applications of stress andstrain resulting from large number of cycles of deformations, includingcompression, compression-extension (elongation), torsion,torsion-compression, torsion-elongation, tension, tension-compression,tension-torsion, etc. The invention gels also exhibit improved damagetolerance, crack propagation resistance and especially improvedresistance to high stress rupture which combination of properties makesthe gels advantageously and surprisingly exceptionally more suitablethan amorphous gels made from non-crystalline poly(ethylene) componentcopolymers at corresponding gel rigidities.

[0114] Block copolymers with polyethylene midblocks alone do not formsuitable Invention gels for purpose of the invention. Crystallizablemidblock regions needs to be balanced with amorphous midblock regions inorder to obtain soft, flexible and elastic gels with the desiredcrystallizable properties that are not found in totally amorphous gels.

[0115] The various representative glassy domain/amorphous structures ofS-E-EB-S, S-E-EB25-S, S-E-EP-E-S, S-EP-E-S and S-EP-E-EP-S. Although thestructure are spheroid representation, cylinders and plates are alsowithin the scope of the present invention. Cylinder and plate structureare obtained with increasing glassy A end blocks. From about 15-30% byweight of A blocks, the block copolymer structure is spheroid. Fromabout 33 about 40% by weight of A blocks, the block copolymer structurebecomes cylindrical; and above about 45% A blocks, the structure becomesless cylindrical and more plate like.

[0116] In order to obtain elastic gels of the invention, it is necessarythat the selective synthesis of butadiene produce sufficient amounts of1,4 poly(butadiene) that on hydrogenation can exhibit “crystallinity” inthe midblocks. In order for the block copolymers forming the inventiongels of the invention to exhibit crystallinity, the crystallizablemidblock segments must contain long runs of —CH₂— groups. There shouldbe approximately 16 units of —(CH₂)— in sequence for crystallinity. Onlythe (—CH₂—)₄ units can crystallize, and then only if there are 4 unitsof (—CH₂—)4 in sequence; alternatively, the polyethylene units aredenoted by [—(CH₂—CH₂—CH₂—CH₂)—]₄, [(—CH₂—)₄]₄ or (—CH₂—)₁₆. The amountof (—CH₂—)₁₆ units forming (E) midblocks of the block copolymerscomprising the invention gels of the invention can be about 20% or lesswhich amount is capable of exhibiting a melting endotherm indifferential scanning calorimeter (DCS) curves.

[0117] The melting exdotherm in DSC curves of the crystallizable blockcopolymers comprising about 20% crystallinity of the polyethyleneportion of the midblock are much higher than conventional amorphousblock copolymers. The poly(ethylene) crystallizable segments ormidblocks of copolymers forming the invention gels of the invention arecharacterized by sufficient crystallinity as to exhibit acrystallization exotherm as determined by DSC curve. The maximum in theendotherm curves of the crystallizable copolymers curs at about lessthan 40° C., but can range from less than about 25° C. to about 60° C.and higher. The crystallizable copolymers forming the invention gels ofthe invention can exhibit crystallization exotherm (as shown by DSC) ofless than about 25° C. to about 75° C. and higher. More specificcrystallization exotherm values of the crystallizable block copolymersinclude: about 8° C., 10° C., 20° C., 28° C., 29° C., 30° C., 31° C.,32° C., 33° C., 34° C., 35° C., 36° C. 37° C., 38° C., 39° C., 40° C.,41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., 49° C.,50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C., 57° C., 58° C.,and higher, whereas, the crystallization exotherm (DSC) for conventionalamorphous midblock segment block copolymers are about 10° C. and lower.

[0118] A sharp crystallization exotherm is seen on cooling. Suchmidblock crystallization endothermic characteristics are missing fromDSC curves of amorphous gels. The fusion endotherm of the crystallizableblock copolymer gels of the invention are determined by ASTM D 3417method.

[0119] Generally, the method of obtaining long runs of crystallizable—(CH2)— is by sequential block copolymer synthesis followed byhydrogenation. The attainment of invention gels of the instant inventionis solely due to the selective polymerization of the butadiene monomer(forming the midblocks) resulting in one or more predetermined amount of1,4 poly(butadiene) blocks followed by sequential polymerization ofadditional midblocks and hydrogenation to produce one or morecrystallizable midblocks of the final block copolymers.

[0120] Hydrogenated polyisoprene midblocks remain amorphous, whilehydrogenated polybutadiene midblocks can be either amorphous orcrystallizable depending upon their structure. Polybutadiene can containeither a 1,2 configuration, which hydrogenates to give the equivalent ofa 1-butene repeat unit, or a 1,4-configuration, which hydrogenates togive the equivalent of an ethylene repeat unit. Polybutadiene midblockshaving approximately 40 weight percent 1,2-butadiene content, based onthe weight of the polybutadiene midblock, provides substantiallyamorphous blocks with low glass transition temperatures uponhydrogenation. Polybutadiene midblocks having less than approximately 40weight percent 1,2-butadiene content, based on the weight of thepolybutadiene midblock, provide crystallizable midblocks uponhydrogenation. The conjugated diene polymer midblock may also be acopolymer of more than one conjugated diene, such as a copolymer ofbutadiene and isoprene. Where the midblock of the block copolymercontains more than one conjugated diene polymer block, such as apolybutadiene block and a polyisoprene block, hence hydrogenatedmidblock can be EB/EP or E/EP depending on the presence and amount ofpolybutadiene 1,2 and 1,4 microstructure.

[0121] The crystallizable block copolymers are made by sequential blockcopolymer synthesis, the percentage of crystallinity or (—CH₂—)₁₆ unitsshould be about (0.67)⁴ or about 20% and actual crystallinity of about12%. For example, a selectively synthesized S-EB_(n)-S copolymer havinga ratio of 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenation willresult in a midblock with a crystallinity of (0.67)4 or 20%. For sake ofsimplicity, when n is a subscript of -EB-, n denotes the percentage of(—CH₂—)₄ units, eg, n=33 or 20% crystallinity which is the percentage of(0.67)₄ or “(—CH₂—)₁₆” units. Thus, when n=28 or 72% of (—CH₂—)₄ units,the % crystallinity is (0.72)₄ or 26.87% crystallinity attributed to(—CH₂—)₁₆ units, denoted by -EB₂₈-. As a matter of convention, and forpurposes of this specification involving hydrogenated polybutadiene: thenotation -E—denotes about 85% of (—CH₂—)₄ units. The notation -B—denotesabout 70% of [—CH₂—CH(C₂H5)—] units. The notation -EB—denotes betweenabout 15 and 70% [—CH₂—CH(C₂H₅)—] units. The notation -EB_(n)—denotes n%[—CH₂—CH(C₂H₅)—] units. For hydrogenated polyisoprene: The notation-EP—denotes about 90% [—CH₂—CH(CH₃)—CH₂—CH₂—] units.

[0122] Generally, one or more (E) midblocks can be incorporated atvarious positions along the midblocks of the block copolymers. Using thesequential process for block copolymer synthesis, the (E) midblocks canbe positioned as follows: A-E-W-A, A-E-W-E-A, A-W-E-W-A,A-E-W-E-W-E-W-E-A, A-W-E-W-A-E-A-E-W-E-A and etc.

[0123] The lower flexibility of block copolymer invention gels due to(E) midblocks can be balanced by the addition of sequentially (W)midblocks. For example, the sequentially synthesized block copolymerS-E-EB-S can maintain a high degree of flexibility due to the presenceof amorphous -EB- block. The sequential block copolymer S-E-EB-B-S canmaintain a high degree of flexibility due to the presence of amorphous-EB- and -B- midblocks. The sequential block copolymer S-E-EP-E-S canmaintain a high degree of flexibility due to the presence of -EP-midblock. The sequential block copolymer S-E-B-S can maintain a highdegree of flexibility due to the presence of the -B- midblock. ForS-E-S, where the midblock is crystallizable and flexibility low,physical blending with amorphous block copolymers such as S-EB-S, S-B-S,S-EP-S, S-EB-EP-S, (S-EP)_(n) and the like can produce more softer, lessrigid, and more flexible invention gel.

[0124] Because of the (E) midblocks, the invention gels of the inventionexhibit different physical characteristics and improvements oversubstantially amorphous gels including damage tolerance, improved crackpropagation resistance, improved tear resistance producing knotty tearsas opposed to smooth tears, improved resistance to fatigue, higherhysteresis, etc. Moreover, the invention gels when stretched exhibitadditional yielding as shown by necking caused by stress inducedcrystallinity. Additionally, the crystallization rates of thecrystallizable midblocks can be controlled and slowed depending onthermal history producing time delay recovery upon deformation.

[0125] Regarding resistance to fatigue, fatigue (as used herein) is thedecay of mechanical properties after repeated application of stress andstrain. Fatigue tests give information about the ability of a materialto resist the development of cracks or crazes resulting from a largenumber of deformation cycles. Fatigue test can be conducted bysubjecting samples of amorphous and invention gels to deformation cyclesto failure (appearance of cracks, crazes, rips or tears in the gels).

[0126] Tensile strength can be determined by extending a selected gelsample to break as measured at 180° U bend around a 5.0 mm mandrelattached to a spring scale. Likewise, tear strength of a notched samplecan be determined by propagating a tear as measured at 180° U bendaround a 50 mm diameter mandrel attached to a spring scale.

[0127] Various block copolymers can be obtained which are amorphous,highly rubbery, and exhibiting minimum dynamic hysteresis:

Block copolymer S-EB-S

[0128] The monomer butadiene can be polymerized in a ether/hydrocarbonsolvent to give a 50/50 ration of 1,2 poly(butadiene)/1,4poly(butadiene) and on hydrogenation no long runs of —CH2— groups andnegligible crystallinity, ie, about (0.5)4 or 0.06 or 6% and actualcrystallinity of about 3%. Due to the constraints of Tg and minimumhysteresis, conventional S-EB-S have ethylene-butylene rations of about60:40 with a crystallinity of about (0.6)₄ or 0.129 or 12% and actualcrystallinity of about 7.7%.

Measuring Gel Rigidities

[0129] One hundred pars by weight of a high viscositypoly(styrene-ethylene-butylene-styrene) triblock copolymer (Shell KratonG 1651) having a styrene end block to ethylene and butylene center blockration of about 33:67 with 0.1 parts by weight of a stabilizer (Irrganox1010) was melt blended with various quantities of a naphthenic oil (ARCOTufflo 6024). Samples having the dimensions of 5 cm×5 cm×3 cm were cutand measured for gel rigidity on a modified Bloom gelometer asdetermined by the gram weight required to depress the gel a distance of4 mm with a piston having a cross-sectional area of 1 cm2. The averagegel rigidity values with respect to various oil concentrations are setforth in Table I below. TABLE I Oil per 100 parts of Gel Rigidity,Triblock copolymer gram Bloom 360 500 463 348 520 280 615 240 635 220710 172 838 135 1,587 54

[0130] With respect to SIS and SEPS, the gel rigidities of approximatelysimilar viscosities, the rigidieties are found to be slightly less thanKraton 1651, whereas for SBS, it is greater and rigidities of SEBS oflower viscosities are slightly greater, but the gels are found to beweaker. For SBEBS, the rigidities are slightly higher. For SEEPS, therigidities are closely similar. Combinations of lower viscosity SEBS andhigher viscosity SEBS, or SEEPS can exhibit greater rigidities. Ingeneral, rigidities appear to vary with polymer viscosity and styrenecontent. In general with some exceptions, the greater the styrenecontent, the greater the rigidity; but is not always the case withreference to polymer viscosity. The rigidity can be less with increasein polymer viscosity. The best methods of determining rigidity is thegram Bloom test any of the gel compositions utilized for PRGC 6 and GFGC2 and 5, while other testing methods will fail to accurately measure therigidity of the gels. The greater midblock segment the lower therigidity.

Block Copolymer S-EP-S

[0131] The monomer isoprene when polymerized will produce 95% 1,4poly(isoprene)/5% 3,4 poly(isoprene) and upon hydrogenation will formamorphous, rubbery poly(ethylene-propylene) midblock and no long runs of—CH2— and no crystallinity.

Mixed Block Copolymer S-EB/EP-S

[0132] The polymerization of a 50/50 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) on hydrogenation will produce a maximumcrystallinity of (0.25)⁴ or 0.4%. The actual crystallinity would beapproximately about 0.2%, which is negligible and results in a goodrubbery midblock.

[0133] The polymerization of a 80/20 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.10)⁴ or 0.01%. The actual crystallinity would beapproximately about 0.006%, which is negligible and results in a goodrubbery midblock.

[0134] The polymerization of a 20/80 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give equal amounts of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.4)4 or 2.56%. The actual crystallinity would beapproximately about 1.53%, which is negligible and results in a goodrubbery midblock.

[0135] The polymerization of a 20/80 mixture of isoprene/butadienemonomers in suitable ether/hydrocarbon solvents to give a 40:60 ratio of1,2 and 1,4 poly(butadiene) will upon hydrogenation produce a lowcrystallinity of (0.48)4 or 5.3%. The actual crystallinity would beapproximately about 3.2%, which is negligible and results in a goodrubbery midblock.

[0136] The midblocks (Z) of one or more -E-, -B-, -EB-, or -EP- cancomprise various combinations of midblocks between the selected endblocks (A); these include: -E-EB-, -E-EP-, B-EP-, -B-EB-, -E-EP-E-,-E-EB-B-, -B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-, -E-EB-EP-,-E-EP-EB-, -B-EB-EP-, -B-EP-EB- and the like.

[0137] The (i) and (v) block copolymers of (A-Z-A) can be obtained bysequential or random synthesis methods followed by hydrogenation of themidblocks. As denoted above, abbreviations are interchangeably used, forexample, (S-E-EP-S) denotespoly(styrene-ethylene-ethylene-co-propylene-styrene). Other linear blockcopolymers (denoted in abbreviations) include the following: (S-E-EB-S),(S-E-EP-S), (S-B-EP-S), (S-B-EB-S), (S-E-EP-E-S), (S-E-E-EB-B-S),(S-B-EP-B-S), (S-B-EB-B-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-EB-EP-S),(S-E-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-EP-S), (S-B-EP-EB-S) and thelike.)_(n)

[0138] The (ii) and (iv) multiblock star-shaped (or radial) copolymers(A-Z)_(n)X can be obtained by sequential synthesis methods includinghydrogenation of selected block copolymers made by polymerizing half ofthe block copolymers such as SBS or SIS and couple the halves with acoupling agent such as an organic dihalide; or couple with an agent suchas SnCl4, which results in star-shaped block copolymers (four branches).Coupling with divinyl benzene give block copolymers which are veryhighly branched. Radial block copolymers suitable for use in forming theinvention gels of the present invention include: (S-E-EB-S)_(n),(S-E-EP)_(n), (S-B-EP)_(n), (S-B-EB)_(n), (S-E-EP-E)_(n),(S-E-EB-B)_(n), (S-B-EP-B)_(n), (S-B-EB-B)_(n), (S-E-B-EB)_(n),(S-E-B-EP)_(n), (S-EB-EP)_(n), (S-E-EB-EP)_(n), (S-E-EP-EB)_(n),(S-B-EB-EP)_(n), ($-B-EP-EB)_(n), (S-E-EP-E-EP)_(n) and the like.

[0139] The selected amount of crystallinity in the midblock should besufficient to achieve improvements in one or more physical propertiesincluding improved damage tolerance, improved crack propagationresistance, improved tear resistance, improved resistance to fatigue ofthe bulk gel and resistance to catastrophic fatigue failure of inventiongel s, such as between the surfaces of the invention gel and substrateor at the interfaces of the interlocking material(s) and invention gel,which improvements are not found in amorphous gels at corresponding gelrigidities.

[0140] As an example, when fabric interlocked or saturated withamorphous S-EB-S gels (gel s) are used as gel liners for lower limb orabove the knee prosthesis to reduce pain over pressure areas and giverelief to the amputee, the commonly used amorphous gels forming theliners can tear or rip apart during marathon race walk after 50-70miles. In extended use, the amorphous gels can rip on the bottom of theliner in normal race walk training of 40-60 miles over a six weeksperiod. In such demanding applications, the invention gels areespecially advantageous and is found to have greater tear resistance andresistance to fatigue resulting from a large number of deformationcycles than amorphous gels. The invention gels are also useful forforming various orthotics and prosthetic articles such as for lowerextremity prosthesis of the L5664 (lower extremity socket insert, aboveknee), L5665 (socket insert, multi-durometer, below knee), L5666 (belowknee, cuff suspension interface), L5667 (below knee, above knee, socketinsert, suction suspension with locking mechanism) type devices asdescribed by the American Orthotic & Prosthetic Association (AOPA)codes. The invention gels are useful for making AOPA code devices forupper extremity prosthetics. The devices can be cast molded or injectionmolded in combination with or without fiber or fabric backing or fiberor fabric reinforcement. When such liners are made without fabricbacking, various gels can be used to form gel-gel and gel-gel-gel s andthe like with varying gel rigidities for the different gel layer(s).Such liners can be made from high viscosity SEBS (such as Kraton 1651and Septon 8006) and moderate viscosity SEBS (Kraton 1654 and Septon8007) block copolymers gels. The add advantage of liners made from SEEPSgels is that such gels exhibit tear and fatigue resistance notachievable using SEBS and SEPS alone.

[0141] Silipos product catalogue (referenced above) which shows a SingleSock Gel Liner product #1272, This and other same but different sizedproducts (#1275 and #1276) were on Public sale. Products #1272 wasoffered for public sale and sold to the public on or about Jan. 31,1995, #1275 was on public sale on or about Jan. 31, 1995, and #1276 wason public sale on or about Dec. 31, 1994. The Single Sock Gel Liner is atube sock-shaped covering for enclosing an amputation stump with a openend for introduction of the stump and a closed end opposite the openend. The liner is a fabric in the shape of a tube sock coated on onlyone side with a gel made from a block copolymer and oil. The gel linersproducts #1272, #1275, and #1276 were on public sale as of the abovementioned dates which products were coated with a block copolymer geldescribed in U.S. Pat. Nos.: 4,369,284 and 4,618,213.

[0142] Selected linear block and radial copolymers utilized in formingthe invention gels of the invention are characterized as having anethylene to butylene midblock ratio (E:B) of about 85:15 to about 65:35.Advantageously, the butylene concentration of the midblock is about 35%or less, more advantageously, about 30% or less, still moreadvantageously, about 25% or less, especially advantageously, about 20%or less. Advantageously, the ethylene to butylene midblock ratios canrange from and in between about 89:11, 88:12, 87:13, 86:14, 85:15,84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25,74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 to about65:35.

[0143] The A to Z midblock ratio of the block copolymers suitable forforming invention gels of the invention can range from about 20:80 to40:60 and higher. More specifically, the values can be and in between:15:85, 19:81, 20:80, 21:79. 22:78. 23:77, 24:76, 25:75, 26:74, 27:73,28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63,38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53,48:52, 49:51, 50:50, 51:49, 52:48, 53:47, 54:46, 55:45, 56:44, 57:43,58:42, 59:41, 60:40, 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 6:33,68:32, 69:31, 70:30 and higher.

[0144] The invention gels can be made in combination with or without aselected amount of one or more selected polymers and copolymers inamounts without substantially decreasing the desired properties. Suchpolymers includes: thermoplastic crystallizable polyurethane elastomerswith hydrocarbon blocks, homopolymers, copolymers, block copolymers,polyethylene, polypropylene, polystyrene, polyethylene copolymers,polypropylene copolymers, and the like. Other (vii) polymers andcopolymers can be linear, star-shaped (radial), branched, or multiarm;these including: (SBS) styrene-butadiene-styrene block copolymers, (SIS)styrene-isoprene-styrene block copolymers, low and medium viscosity(S-EB-S) styrene-ethylene-butylene-styrene block copolymers, (S-EP)styrene-ethylene-propylene block copolymers, (S-EP-S)styrene-ethylene/propylene-styrene block copolymers, (S-E-EPS)styrene-ethylene-ethylene/propylene-styrene block copolymers, (SB)_(n)styrene-butadiene and (S-EB)_(n), (S-EB-S)_(n), (S-E-EP)_(n), (SEP)_(n),(SI)_(n) multiarm, branched or star-shaped copolymers, polyethyleneoxide(EO), poly(dimethylphenylene oxide), teflon (TFE, PTFE, PEA, FEP, etc),optical clear amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole (PDD) andtetrafluoroethylene (TFE), maleated S-EB-S block copolymer,polycarbonate, ethylene vinyl alcohol copolymer, ethylene/styreneinterpolymers, and the like. Still, other polymers include homopolymerswhich can be utilized in minor amounts; these include: polystyrene,polydimethylsiloxane, polyolefins such as polybutylene, polyethylene,Hoechst Celanese/PEG 20000 UHMW polyethylene (Mw=1,000,000-6,000,000),polyethylene copolymers, polypropylene, silicone (Tospearl 120A, 145Aetc) and the like. Polyurethane thermoplastic crystallizable copolymerswith hydrocarbon midblocks based on saturated hydrocarbon diols(Handlin, D., Chin. S., and Masse. M., et al. “POLYURETHANE ELASTOMERSBASED ON NEW SATURATED HYDROCARBON DIOLS” Published Society of PlasticsIndustry, Polyurethane Division, Las Vegas, Oct. 23, 1996) are alsosuitable for use in blending with the block copolymers (i-vi) used informing the invention gels of the invention. Such saturated hydrocarbondiols include hydroxyl terminated oligomers of poly(ethylene-butylene)(EB), poly(ethylene-propylene) (EP),-E-EB-, -E-EP-, -B-EP-, -B-EB-,-E-EP-E-, -E-EB-B-, -B-EP-B-, -B-EB-B-, -E-B-EB-, -E-B-EP-, -EB-EP-,-E-EB-EP-, -E-EP-EB-, -B-EB-EP-, -B-EP-EB-, -E-EP-E-EP-, -E-EP-E-EB-,-B-EP-B-EP-, -B-EB-B-EB- and the like. As an example, thermoplasticpolyurethane made with isocyanates and chain extenders such as TMPD andBEPD from saturated hydrocarbon diol KLP L-2203 having a hard segmentcontents of 22% exhibits clean phase separation of the hard and softsegments with glass a transition of −50° C. KLP L-2203 based TPU's canbe mixed with the crystallizable block copolymers to form soft inventiongels within the gel rigidity ranges of the invention.

[0145] As described in U.S. Patent Application 20020061982 andincorporated herein by reference, ethylene/styrene interpolymers areprepared by polymerizing i) ethylene or one or more alpha-olefinmonomers and ii) one or more vinyl or vinylidene aromatic monomersand/or one or more sterically hindered aliphatic or cycloaliphatic vinylor vinylidene monomers, and optionally iii) other polymerizableethylenically unsaturated monomer(s).

[0146] Ethylene/styrene interpolymers can be substantially random,psuedo-random, random, alternately, diadic, triadic, tetradic or anycombination thereof. That is, the interpolymer product can be variablyincorporated and optionally variably sequenced. Ethylene/styreneinterpolymers are substantially random ethylene/styrene interpolymers.

[0147] The high glassy component (viii) copolymers suitable for use informing the invention gels of the invention include high styrenecomponent BASF's Styroflex series copolymers including BX 6105 with astatistical SB sequence for the low elastomeric segments (styrene tobutadiene ratio of 1:1) and an overall styrene content of almost 70%,high styrene content Shell Kraton G, Kraton D-1122X (SB)_(n), D-4122SBS, D-4240 (SB)_(n), D4230 (SB)_(n), DX-1150 SBS, D-4140 SBS, D-1115SBS, D-4222 SBS, Kraton D-1401P, SEBS, Dexco's Vector 6241-D, 4411-D,Fina's Finaclear high styrene content SBS series copolymers, PhillipsPetroleum's XK40 K-Resin styrene/butadiene copolymers, Kuraray's S2104SEPS. The (viii) copolymers include amorphous polymers with high styrenecontent: SBS, SIS, SEPS, SEB/EPS and the like. The copolymers withglassy to elastomeric ratios (S:EB, S:EP, S:I, S:B, S:EEP, S:BB,S:EB/EP, S:IB, S:EBB and the like) can range from and in between 25:75,26:74, 27:73, 28:72, 29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65,36:64, 37:63, 37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57,44.65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49 52:48, 53:47,54:46, 55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 6:39, 62:38, 63:37,64:36, 65:35, 66:34, 67:33, 68:32, 69:31, 70:30, 7:29, 72:28, 73:27,74:26, 75:25, 76:24, 77:23, 78:22, 79:21, to 80:20 and higher.

[0148] Suitable polyolefins include polyethylene and polyethylenecopolymers such as Dow Chemical Company's Dowlex 3010, 2021D, 2038,2042A, 2049, 2049A, 2071, 2077, 2244A, 2267A; Dow Affinity ethylenealpha-olefin resin PL-1840, SE-1400, SM-1300; more suitably: Dow Elite5100, 5110, 5200, 5400, Primacor 141-XT, 1430, 1420, 1320, 3330, 3150,2912, 3340, 3460; Dow Attane (ultra low density ethylene-octene-1copolymers) 4803, 4801, 4602, Eastman Mxsten CV copolymers of ethyleneand hexene (0.905-0.910 g/cm3).

[0149] The conventional term “major” means about 51 weight percent andhigher (e.g. 55%, 60%, 65%, 70%, 75%, 80% and the like) and the term“minor” means 49 weight percent and lower (e.g. 2%, 5%, 10%, 15%, 20%,25% and the like).

[0150] Representative plasticizer oil gels (polymer+oil) of theinvention include: (a) Kraton G 1651, G 1654X gels; (b) Kraton G 4600gels; (c) Kraton G 4609 gels; other suitable high viscosity polymer andoil gels include: (d) Tuftec H 1051 gels; (e) Tuftec H 1041 gels; (f)Tuftec H 1052 gels; (g) Kuraray SEEPS 4055 gel; (h) Kuraray SEBS 8006gel; (i) Kuraray SEPS 2005 gel; (j) Kuraray SEPS 2006 gel, and (k) Gelsmade from blends (polyblends) of (a)-(h) with other polymers andcopolymers include: (1) SEBS-SBS gels; (2) SEBS-SIS gels; (3) SEBS-(SEP)gels; (4) SEBS-(SEB)_(n) gels; (5) SEBS-(SEB)_(n) gels; (6)SEBS-(SEP)_(n) gels; (7) SEBS-(SI)_(n) gels; (8) SEBS-(SI) multiarmgels; (9) SEBS-(SEB)_(n) gels; (10) (SEB)_(n) star-shaped copolymergels; (11) gels made from blends of (a)-(k) with other homopolymersinclude: (12) SEBS/polystyrene gels; (13) SEBS/polybutylene gels; (14)SEBS/polyethylene gels; (14) SEBS/polypropylene gels; (16) SEP/SEBS oilgels (17), SEP/SEPS oil gels (18), SEP/SEPS/SEB oil gels (19),SEPS/SEBS/SEP oil gels (20), SEB/SEBS (21), EB-EP/SEBS (22), SEBS/EB(23), SEBS/EP (24), (25) (SEB)_(n) gels, (26) (SEP)_(n) gels, (27) SEEPSgels, and the like.

[0151] Representative examples of commercial elastomers that can beformed with plasticizing oils in combination with the high viscositytriblock and branched copolymers described above into suitable gels foruse in making the gel compositions and articles of the invention: ShellKratons D1101, D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, D1117,D118X, D1122X, D1125X, D1133X, D1135X, D1184, D1188X, D1300X, D1320X,D4122, D4141, D4158, D4240, G1650, G1652, G1657, G1701X, G1702X, G1726X,G1750X, G1765X, FG1901X, FG1921X, D2103, D2109, D2122X, D3202, D3204,D3226, D5298, D5999X, D7340, G1654X, G2701, G2703, G2705, G1706, G2721X,G7155, G7430, G7450, G7523X, G7528X, G7680, G7705, G7702X, G7720,G7722X, G7820, G7821X, G7827, G7890X, G7940. Kuraray's SEEPS, SEP/SEPSor SEP/SEB/SEPS Nos. 1001, 1050, 2002, 2003, 3023, 2007, 2043, 2063,2050, 2103, 2104 (SEPS with a high styrene content of 65), 2105, 4033(SEEPS), 4044 (SEEPS), 4045 (SEEPS), 4077 (SEEPS), 4099 (SEEPS), 8004(SEBS), 8007, H-VS-3 (S-V-EP)_(n), Dexco polymers (Vector): 4411, 4461,6241, DPX555, tuftec-P series SBBS (styrene-butadiene-butylene-styrene)and the like.

[0152] The Kuraray SEPTON 4000 (SEEPS) series block polymers: 4033,4044, 4055, 4045, 4077, 4099, and the like useful in making the gels ofthe instant invention are made from hydrogenated styreneisoprene/butadiene styrene block copolymer or more specifically madefrom hydrogenated styrene block polymer with 2-methyl-1,3-butadiene and1,3-butadiene. Such poly(styrene-isoprene/butadiene-styrene) polymers,depending on the butadiene structure, when hydrogenated will result in“(SEB/EPS)”. In cases where the butadiene structures are controlled, itis appropriate to denote (SEB/EPS) as (SE/EPS) where E/EP isethylene-ethylene-propylene or more simply as (SEEPS) to indicate thatthe ethylene (E) of the ethylene-butylene (EB) segment of the midblock(EB/EP) of the (SEB/EPS) block polymer is substantially greater thanbutylene (B) and the amount of (E) can be sufficient so as to exhibitethylene crystallinity. As indicated below, it is the presence orabsence of the butylene methyl group which can be use to distinguish theSEBS polymer from the SEPS and SEEPS types of polymer. The SEEPS polymerof the invention gel, within the experimental uncertainty, lackssufficient butylene. The invention gels can comprise (I) SEEPS polymersand other (II) polymers, such as: SEPS, SEBS, SIS, SBS, SEB/EPS and thelike.

[0153] As taught in my co-pending application Ser. Nos. 10/273,828 and10/1,999,364, and specifically incorporated herein, the unusualproperties of the invention SEEPS gels can be attributed to alteringdifferent phase or interfacial arrangements of the domains of themultiblock copolymers. The presence of polyethylene and crystallinity inblock copolymers can be determined by NMR and DSC.

[0154] Physical measurements (NMR and DSC) of typical commercial KratonG 1651, Septon 2006, Septon 4033 and Septon 4055 block were performed.Two types of 13C NMR spectra data were collected. The gated decoupledexperiment provided quantitative data for each type of carbon atom. TheDEPT experiment identified each type of carbon atom having attachedprotons. The DEPT data allowed assignment of the resonances in the gateddecoupled experiment, which was then integrated for quantitation of thedifferent types of midblock and end groups in each polymer tested

[0155] The relative quantities of each type of carbon group in thevarious polymers were found. The uncertainty associated with thesemeasurements is estimated as +3 percentage units. Only the Kraton 1651spectrum had resonances below about 20 ppm. These resonances, at10.7-10.9 ppm, were assigned to the butylene methyl group anddistinguish the SEBS polymer from the SEPS and SEEPS types of polymer.Only the Septon 2006 spectrum lacked the resonance at about 20 ppm thatis characteristic of polyethylene units (defined here as threecontiguous CH2 groups), and this feature distinguishes the SEPS polymerfrom the SEBS and SEEPS polymers. There were additional differencesbetween the spectra. The Septon 2006 and the Septon 4033 and 4055spectra all showed resonances at 20 ppm; whereas the spectrum of Kraton1651 was missing this resonance. The 20 ppm peak is characteristic ofthe methyl group of a propylene subunit, which is present in SEPS andSEEPS polymers but absent in the SEBS polymer. There were also amethylene peak, at 24.6 ppm, and a methine peak at 32.8 ppm, in all ofthe Septon spectra but not in the Kraton 1651 spectra. These resonancesalso arise from the propylene subunit.

[0156] The chemical shifts, relative intensities, and relativeintegrations were the same for the spectra of the Septon 4033 and Septon4055, indicating that these two polymeric compositions are identicalbased on NMR spectroscopy.

[0157] DSC of ASTM D3417-99 was modified to provide conditions for thesamples to have the best possible chance to exhibit any crystallinity.The protocol was as follows: (1) heat to 140° C. @ 10° C./min., (2) coolto 0° C. @ 2° C./min., (3) place in freezer for (1) week, (4) heat to140° C. @ 1° C./min, and (5) cool to 0° C @ 1° C./min.

[0158] This protocol was used with the exception that the samples wereleft in the freezer for approximately 2 months, instead of 1 week,because the DSC equipment broke during the week after the first run andrequired some time for repair. This delay is not expected to havenegatively impacted the results of the experiment.

[0159] Two HDPE reference samples gave clearly defined crystallizationexotherms and fusion endotherms, allowing calculation of heats ofcrystallization and fusion. These results showed that the equipment andmethodology were fully functional, and this check was performed dailyduring DSC operation. Of the samples, only Kraton 1651 showeddiscernible transitions for both crystallization and fusion. The Septon2006 showed no discernible transitions, which is consistent with itsSEPS structure being entirely amorphous. The Septons 4033 and 4055showed crystallization exotherms.

[0160] The heats of crystallization for the Kraton 1651 and Septons 4033and 4055 were small, below about 3 J/g, indicating that small amounts ofcrystallinity are present in these polymers. The DSC data show:

[0161] Kraton 1651: crystallization exotherm peak at 18.09° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 1.43, fusionendotherm peak at 34.13° C., and Fusion Endotherm—mass normalizedenthalphy J/g of 15.17.

[0162] Septon 2006: crystallization exotherm peak (not detected),crystallization exotherm—mass normalized enthalpy (not detected), fusionendotherm peak NONE, and Fusion Endotherm—mass normalized enthalphy (notdetected).

[0163] Septon 4033: crystallization exotherm peak at 2.86° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 3.00, fusionendotherm peak (not detected), and Fusion Endotherm—mass normalizedenthalphy (not detected).

[0164] Septon 4055: crystallization exotherm peak at 14.4° C.,crystallization exotherm—mass normalized enthalpy (J/g) of 1.32, fusionendotherm peak (not detected), and Fusion Endotherm—mass normalizedenthalphy (not detected).

[0165] Aldrich 13813JU polyethylene reference: crystallization exothermpeak at 119.72° C., crystallization exotherm—mass normalized enthalpy(J/g) of 174.60, fusion endotherm peak at 130.70° C., and FusionEndotherm—mass normalized enthalphy J/g of 189.90.

[0166] The invention gels made from higher viscosity SEEPS copolymers(I) are resistant to breaking when sheared than SEPS triblock copolymergels. This can be demonstrated by forming a very soft gel, for example100 parts copolymer to 800 parts plasticizing oil. The soft gel is cutinto a strip of 2.5 cm×2.5 cm cross-section, the gel strip is grippedlengthwise tightly in the left hand about its cross-section and anexposed. part of the gel strip being gripped lengthwise around itscross-section tightly by the right hand as close to the left hand aspossible without stretching. With the two hands gripping the gel strip'scross-section, the hands are moved in opposite directions to shear apartthe gel strip at its cross-section. The shearing action by the grippinghands is done at the fastest speed possible as can be performed by humanhands. The shearing action is performed at a fraction of a second,possible at about 0.5 seconds. Using this demonstration, the SEEPScopolymer (I) invention gels will not easily break completely apart aswould gels formed from SEPS triblock copolymers. In some cases, it willtake two, three, or more attempts to shear a high viscosity copolymer(I) gel strip this way. Whereas, a lower viscosity triblock copolymergel strip can be sheared apart on the first try. For gels made fromcopolymers with viscosities of 5 wt % solution in Toluene of from lessthan 2 mPa-S to 500 mPa-S and higher, their shear resistance willdecrease with decreasing viscosity.

[0167] Hence, it is the selected SEEPS which provides the improved tearand fatigue resistance of the invention gel compositions and articles.SEEPS gels of corresponding rigidity exhibit improved greater tear andgreater fatigue resistance over SEPS gels and SEBS gels.

[0168] As taught in my co-pending application Ser. Nos. 09/721,213;09/130,545; 10/273,828; 09/517,230; 09/412,886; 10/1,999,364 andspecifically incorporated herein, tear strength and resistance tofatigue of the high viscosity SEEPS gels of the invention atcorresponding rigidities are found to be greater than that of SEPS gels.Greater tear and fatigue resistance is also found when SEEPS gels aremade in combination with other (II) polymers, such as SEPS, SEBS, SBS,SIS, low viscosity SEBS, lower viscosity SEEPS, PS, PE, PP, (SI)_(n),(SB)_(n), (SEB)_(n), Ashai SB/EBSpoly(styrene-butadiene-ethylene-butylene-styrene), and the like.

[0169] The amorphous S-EB-S and (S-EB)_(n) copolymers can have a broadrange of styrene to ethylene-butylene ratios (S:EB) of about 20:80 orless to about 40:60 or higher. The S:EB weight ratios can range fromlower than about 20:80 to above about 40:60 and higher. Morespecifically, the values can be from and in between: 15:85, 19:81,20:80, 21:79. 22:78. 23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71,30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, (and higher ratios forviii copolymers) 37:63, 37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58,43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49 52:48 andetc. Other ratio values of less than 19:81 or higher than 51:49 are alsopossible. Broadly, the styrene block to elastomeric block ratio of thehigh viscosity liner and star copolymers is about 20:80 to about 40:60or higher, less broadly about 31:69 to about 40:60, preferably about32:68 to about 38:62, more preferably about 32:68 to about 36:64,particularly more preferably about 32:68 to about 34:66, especially morepreferably about 33:67 to about 36:64, and still more preferably about30:70.

[0170] The Brookfield Viscosity of a 5 weight percent solids solution intoluene at 30° C. of 2006, 4033, 4045, 4055, and 4077 typically rangeabout 20-35, about 25-150, about 60-150, about 200-400 respectively.Typical Brookfield Viscosities of a 10 weight percent solids solution intoluene at 30° C. of 1001, 1050, 2007, 2063, 2043, 4033, 2005, 2006, areabout 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. TypicalBrookfield Viscosity of a 25 weight percent solids solution in tolueneat 25° C. of Kraton D1101, D1116, D1184, D1300X, G1701X, G1702X areabout 4000, 9000, 20000, 6000, 50000 and 50000 cps respectively. TypicalBrookfield Viscosity of a 10 weight percent solids solution in tolueneat 25° C. of G1654X is about 370 cps. The Brookfield Viscosities of a 20and 30 weight percent solids solution in toluene at 30° C. of H-VS-3 areabout 133 cps and 350 cps respectively.

[0171] Suitable block copolymers and their typical viscosities arefurther described. Shell Technical Bulletin SC:1393-92 gives solutionviscosity as measured with a Brookfield model RVT viscometer at 25° C.for Kraton G 1654X at 10% weight in toluene of approximately 400 cps andat 15% weight in toluene of approximately 5,600 cps. Shell publicationSC:68-79 gives solution viscosity at 25° C. for Kraton G 1651 at 20weight percent in toluene of approximately 2,000 cps. When measured at 5weight percent solution in toluene at 30° C., the solution viscosity ofKraton G 1651 is about 40. Examples of high viscosity S-EB-S triblockcopolymers includes Kuraray's S-EB-S 8006 which exhibits a solutionviscosity at 5 weight percent at 30° C. of about 51 cps. Kuraray's 2006SEPS polymer exhibits a viscosity at 20 weight percent solution intoluene at 30° C. of about 78,000 cps, at 5 weight percent of about 27cps, at 10 weight percent of about 1220 cps, and at 20 weight percent78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 5 weightpercent solution in toluene at 30° C. of about 28 cps, at 10 weightpercent of about 1200 cps, and at 20 weight percent 76,000 cps. Othergrades of S-EB-S, SEPS, (SEB)_(n), (SEP)_(n) polymers can also beutilized in the present invention provided such polymers exhibits therequired high viscosity. Such S-EB-S polymers include (high viscosity)Kraton G 1855X which has a Specific Gravity of 0.92, BrookfieldViscosity of a 25 weight percent solids solution in toluene at 25° C. ofabout 40,000 cps or about 8,000 to about 20,000 cps at a 20 weightpercent solids solution in toluene at 25° C.

[0172] The styrene to ethylene and butylene (S:EB) weight ratios for theShell designated polymers can have a low range of 20:80 or less.Although the typical ratio values for Kraton G 1651, 4600, and 4609 areapproximately about 33:67 and for Kraton G 1855X approximately about27:73, Kraton G 1654X (a lower molecular weight version of Kraton G 1651with somewhat lower physical properties such as lower solution and meltviscosity) is approximately about 31:69, these ratios can vary broadlyfrom the typical product specification values. In the case of Kuraray'sS-EB-S polymer 8006 the S:EB weight ratio is about 35:65. In the case ofKuraray's 2005 (SEPS), and 2006 (SEPS), the S:EP weight ratios are 20:80and 35:65 respectively. The styrene to ethylene-ethylene/propylene(S:EB-EP) ratios of Kuraray's SEPTON 4033, 4045, 4055, and 4077 aretypically about 30, 37.6, 30, 30 respectively. More typically the(S:EB-EP) and (S:EP) ratios can vary broadly much like S:EB ratios ofS-EB-S and (SEB)_(n) from less than 19:81 to higher than 51:49 (asrecited above) are possible. It should be noted that multiblockcopolymers including SEPTON 4033, 4044, 4045, 4055, 4077, 4099 and thelike are described in my cited copending parent applications and are thesubject matter of related inventions.

[0173] The block copolymers such as Kraton. G 1654X having ratios of31:69 or higher can be used and do exhibit about the same physicalproperties in many respects to Kraton G 1651 while Kraton G 1654X withratios below 31:69 can also be use, but they are less advantageous dueto their decrease in the desirable properties of the final gel.

[0174] Plasticizers particularly advantageous for use in practicing thepresent invention are will known in the art, they include rubberprocessing oils such as paraffinic and naphthenic petroleum oils, highlyrefined aromatic-free paraffinic and naphthenic food and technical gradewhite petroleum mineral oils, and synthetic liquid oligomers ofpolybutene, polypropene, polyterpene, etc. The synthetic series processoils are high viscosity oligomers which are permanently fluid liquidnonolefins, isoparaffins or paraffins of moderate to high molecularweight.

[0175] Selected amounts of any compatible plasticizers can be utilizedin forming the invention gels of the invention, but because of thenon-tack property of the invention gels of the invention, the majoramount of plasticizers used should be low viscosity plasticizers havingviscosities advantageously of not greater than about 30 cSt @ 40° C.

[0176] Examples of representative commercially available plasticizingoils include Amoco® polybutenes, hydrogenated polybutenes, polybuteneswith epoxide functionality at one end of the polybutene polymer, liquidpoly(ethylene/butylene), liquid hetero-telechelic polymers ofpoly(ethylene/butylene/styrene) with epoxidized polyisoprene andpoly(ethylene/butylene) with epoxidized polyisoprene: Example of suchpolybutenes include: L-14 (320 Mn), L-50 (420 Mn), L-100 (460 Mn), H-15(560 Mn), H-25 (610 Mn), H-35 (660 Mn), H-50 (750 Mn), H-100 (920 Mn),H-300 (1290 Mn), L-14E (27-37 cst @ 100° F. Viscosity), H-300E (635-690cst @ 210° F. Viscosity), Actipol E6 (365 Mn), E16 (973 Mn), E23 (1433Mn), Kraton L-1203, EKP-206, EKP-207, HPVM-2203 and the like. Example ofvarious commercially oils include: ARCO Prime (55, 70, 90, 200, 350, 400and the like), Duroprime and Tufflo oils (6006, 6016, 6016M, 6026, 6036,6056, 6206, etc), other white mineral oils include: Bayol, Bernol,American, Drakeol, Ervol, Gloria, Kaydol, Litetek, Lyondell (Duroprime55, 70, 90, 200, 350, 400, Ideal FG 32, 46, 68, 100, 220, 460), Marcol,Parol, Peneteck, Primol, Protol, Sontex, and the like. Oils useful inthe invention gel include: Witco 40 oil, Ervol, Benol, Blandol,Semtol-100, Semtol 85, Semtol 70, Semtol 40, Orzol, Britol, Protol,Rudol, Carnation, Klearol; 350, 100, 85, 70, 40, Pd-23, Pd 25, Pd28, FG32, 46, 68, 100, 220, 460, Duroprime Ds-L, Ds-M, Duropac 70, 90, Crystex22, Af-L, Af M, 6006, 6016, 6026, Tufflo 6056, Ste Oil Co, Inc:Invention Plus 70, 200, 350, Lyondell: Duroprime DS L & M, Duropac 70,90, Crystex 22, Crystex AF L & M, Tufflo 6006, 6016; Chevron TexacoCorp: Superta White Oil 5, Superta 7, 9, 10, 13, 18, 21, 31, 35, 38, 50,Penreco: Conosol 340, Conosol C-200, Drakeol 15, 13, 10, 10B, 9, 7, 5,50, Peneteck, Ultra Chemical Inc, Ultraol White 60Nf, Ultraol White50Nf, Witco Hydrobrite 100, 550, 1000, and the like.

[0177] Selected amounts of one or more compatible plasticizers can beused to achieve gel rigidities of from less than about 2 gram Bloom toabout 1,800 gram Bloom and higher. Tack may not completely be dependentupon the amount of the glassy phase, by using selected amount of certainlow viscosity oil plasticizers, block copolymers of SEBS, SEEPS, SEPS,SEPn, SEBn, and the like, gel tack can be reduced or the gel can be madenon-tacky.

[0178] Major or minor amounts (based on 100 parts by weight of baseelastomer) of any compatible second plasticizers can be utilized informing the invention gel, but because of the non-tack property of theinvention gel, the major amount of first plasticizers used should be lowviscosity plasticizers having viscosities advantageously of not greaterthan about 30 cSt @ 40° C., for example values and in between: 30, 29,28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11,10, 9, 8, 7, 6, 5, 4, 3 and the like. Such low viscosity plasticizersare commercially available as, for example, from Witco: Rudol, Ervol,Benol, Blandol, Carnation, Klearol, Semtol100, Semtol 85, Semtol 70,Semtol 40; from Lyondell: Duroprime 55, 70, 90, Duroprime DS L & M,Duropac 70, 90, Crystex 22, Crystex AF L & M, Tufflo 6006, 6016 and thelike. The invention gel tack decreases with decreasing oil viscositiesof from about 30 to 3. Invention gels which are non-tacky to the touchcan be achieved using oils with viscosities of about 10 cSt @ 40° C. andless. Best result can be achieved using oils with viscosities of about 6and less. Oils of higher viscosities of from about 500 cSt @ 40° C. toabout 30 produce higher and higher tack with increase in viscosities.Heat temperature set resistance improves with increase in oil viscosity.Oils with viscosities less than about 15 exhibit heat set at about 50°C. Therefore a combination of low viscosity oils to improve low tack andhigh viscosity oils to improve set can be achieved by blending variousoils having the desired viscosities for the desired end use. Thedisassociation of polystyrene is about 100° C. to about 135° C., theinvention gels do not melt below the disassociation temperature ofpolystyrene. It is important that fishing bait when stored in a fishingbox in the hot Sun at about 50° C. to about 58° C. do not suffersubstantial heat set as tested at these temperatures in a 108° U bendfor one hour.

[0179] It has been found that the lower the oil viscosity, the lower theheat set of the resulting gel composition and the higher the oilviscosity use in the gel compositions of the invention, the higher theheat set of the resulting gel composition. For example, if the firstplasticizer is less than about 50 SUS @ 100° F., the heat set of theresulting gel composition comprising 100 parts of (I) copolymers ofequal parts of SEEPS 4055 and Kraton G 1651 with about 600 parts byweight of the first plasticizer, the resulting is found to have a heatset less than that of a conventional PVC plastisol fishing bait at about50° C. However, as the 50 Vis SUS @ 100° F. oil of the formulation isgradually replaced with a higher viscosity oil of about 80-90 SUS @ 100°C., the heat set deformation improves with increasing amounts of thehigher viscosity oil. In order to obtain equal heat set performance asconventional PVC plastisol fishing bait, the first and secondplasticizers would have to be of equal amounts in the gel composition.Replacing the first plasticizer with a greater amount would increase thegel tack. If tack is not of great concern, then a higher amount of thesecond plasticizers would be beneficial for improving heat set at higherand higher temperatures to the point that the second plasticizers canreach greater than 2525 SUS @ 100° C. (Ideal FG 100, 220, or 460 oil)the resulting gel composition would not exhibit set at even temperaturesgreater than 400° F.

[0180] The cited first plasticizers with or without one or more secondplasticizers can be used in sufficient amounts to achieve a gel rigidityof from about 20 gram Bloom to about 1,800 gram Bloom. The secondplasticizers in effective amounts in combination with the firstplasticizers can provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the firstplasticizers alone. The second plasticizers when used can provide agreater temperature compression set than a gelatinous composition havingthe same rigidity formed from the first plasticizers alone or formedfrom a combination of the first plasticizers and the secondplasticizers. The first plasticizers being in effective amounts withsaid second plasticizers can provide a Gram Tack lower than a gelatinouscomposition having the same rigidity formed from the second plasticizersalone.

[0181] Generally, plasticizing oils with average molecular weights lessthan about 200 and greater than about 700 may also be used (e.g. H-300(1290 Mn)). It is well know that minor and sufficient amounts of VitaminE is added to the described commercially available oils during bulkprocessing which is useful as a oil stabilizer, antioxidant, andpreservative.

[0182] Of all the factors, the amount of plasticizing oils can becontrolled and adjusted advantageously to obtain substantially highertear and tensile strength gels. The improvements in tensile strength ofthe invention gels are accompanied by corresponding increase in gelrigidity as the amount of plasticizing oils are lowered until therigidity of the invention gels becomes much higher than that of the gumswhich surround the teeth. Although higher tensile strengths can beobtained as the amount of plasticizing oils in the gel approaches zero,the tensile strength of the floss, however, must be maintained at anacceptable gel rigidity (at sufficient high plasticizing oil levels) inorder to be as soft as the gums required for flossing. For example, therigidities of a gel containing 100, 200, or 300 parts by weight of oilis much higher than a gel containing 300, 400, 500, 600, 800, or 900parts of oil.

[0183] These gels can exhibit a larger unit lateral contraction at thesame elongation per unit of length as their counterpart parent gels fromwhich the invention gels are derived or formed. This property wouldallow a same unit volume of gel when elongated as its parent to easilywedge between the teeth when flossing. It would seem that a gel havingthe 1.0 cm3 volume made from a ratio of 100 parts by weight of copolymerand 400 parts plasticizer would have a unique macro volumeconfigurations that is at equilibrium with the plasticizer which is muchlike a 3-D fingerprint which is uniquely different from any other gel ofa different copolymer to plasticizer ratio. Reducing the plasticizercontent of a ratio 100:400 gel to a 100:300 ratio of copolymer toplasticizer will decrease the amount of plasticizer, but the originalmacro volume configurations will remain the same.

[0184] Speculative theories not withstanding, configurations may takethe form of (1) Swiss cheese, (2) sponge, (3) the insides of a loaf ofbread, (4) structures liken to ocean brain corals, (5) large structuresand small structures forming the 3-D gel volume landscape, (6) the outerheated surface which cools faster than the inner volumes of the gelduring its cooling histories may have a patterned crust (rich in Amicro-phases) like that of a loaf of bread and the inner volume may havemuch like 1-5, and (7) the many different possible structures areunlimited and volume landscapes may be interconnected at the macro levelby threads or micro-strands of Z micro-phases.

[0185] The amount of plasticizer extracted can advantageously range fromless than about 10% by weight to about 90% and higher of the totalweight of the plasticizer. More advantageously, the extracted amounts ofplasticizer can range from less than about 20% by weight to about 80% byweight of the total plasticizer, and still more advantageously, fromabout 25% to about 75%. Plasticizing oils contained in the inventiongels can be extracted by any conventional methods, such as solventextraction, physical extraction, pressure, pressure-heat, heat-solvent,pressure-solvent-heat, vacuum extraction, vacuum-heat extraction,vacuum-pressure extraction, vacuum-heat-pressure extraction,vacuum-solvent extraction, vacuum-heat-solvent-pressure extraction, etc.The solvents selected, should be solvents which do not substantiallydisrupt the A and Z phases of the (I) copolymers forming the inventiongels. Any solvent which will extract plasticizer from the gel and do notdisrupt the A and Z phases can be utilized. Suitable solvents includealcohols, primary, secondary and tertiary alcohols, glycols, etc.,examples include methanol, ethanol, tetradecanol, etc. Likewise, thepressures and heat applied to remove the desired amounts of oils shouldnot be sufficient to disrupt the A and Z domains of the (I) copolymers.To form a lower rigidity gel, the simplest method is to subject the gelto heat in a partial vacuum or under higher vacuum for a selected periodof time, depending on the amount of plasticizer to be extracted.

[0186] Surprisingly, as disclosed in my application Ser. No. 09/896,047filed Jun. 30, 2001, oil extraction from the invention gels can beachieved with little or no energy in the presence of one or moresilicone fluids to almost any degree. A theory can be made to explainthe physics involved in the extraction process which reasoning is asfollows: (1) When water is placed in contact with an oil extended gel,the gel will not over time exhibit weight loss. (2) When oil is add to acolumn of water in a test tube, the oil will separate out and find itslevel above the column of water. (3) The surface tension of water at 25°C. is about 72.0 mN/m. (4) The surface tension of oil (mineral oil) at25° C. is about 29.7 mN/m. (5) The surface tension of silicone fluid at25° C. range from abut 16 to abut 22 mN/m (for example: the surfacetension of 100 cSt silicone fluid at STP is 20.9 mN/m). (6) The densityof oil is less than the density of silicone fluid, silicone grease,silicone gel, and silicone elastomer. (7) Oil is not a polar liquid andis highly compatible with the rubber phase of the oil gel formingpolymer. (8) Silicone is polar and not compatible with the polymer'srubber phase.

[0187] The molecules of a liquid oil drop attract each other. Theinteractions of an oil molecule in the liquid oil drop are balanced byan equal attractive force in all directions. Oil molecules on thesurface of the liquid oil drop experience an imbalance of forces at theinterface with air. The effect is the presence of free energy at thesurface. This excess energy is called surface free energy and isquantified as a measurement of energy/area. This can be described astension or surface tension which is quantified as a force/lengthmeasurement or m/Nm.

[0188] Clearly gravity is the only force pulling on the extracted oilfrom the gel in the presence of silicone fluid at the gel-petri dishinterface in the examples below. In the case of gel samples in the petridishes in contact with silicone fluids, the extracted oil are collectedon the top surface layer of the silicone fluid while the silicone fluidmaintain constant contact and surrounds the gel sample. In the case ofgel placed in a test tube of silicone fluid of different viscosity, theoil is extracted and migrates and collect at the top of the siliconefluid surface while the gel reduces in volume with time. The oilextraction process in silicone is accompanied by buoyant forces removingthe extracted oil from the surroundings of the gel constantlysurrounding the gel with fresh silicone fluid while in the example ofalcohol, since the oil is heavier, the oil is maintained and surroundsthe gel sample forming a equilibrium condition of oil surround the gelsample while keeping the alcohol from being in contact with the gelsample. Therefore in order to use alcohol to extract oil from a gelsample, the extracted oil must be constantly removed from the oilalcohol mixture as is the case during soxhlet extraction which processrequires additional energy to pump the oil-alcohol mixture away from thesample and removing the oil before forcing the alcohol back to the gelsample surface to perform further extraction.

[0189] Silicone fluid is efficient and useful for extracting oil formoil gel compositions with the assistance of gravity and buoyancy of oilin the silicone fluids.

[0190] It is very difficult to extract, separate, or remove oil from anoil gel composition by positive or vacuum pressure or heat while usinglittle or no energy and because of the affinity of the rubber midblockfor oil, not even the weight of a two ton truck resting on a four squarefoot area (placing a layer of gel between four pairs of one foot squareparallel steel plates one set under each of the truck tire resting onthe gels) can separate the oil from the gel composition.

[0191] The use of silicone fluids of various viscosity acts as a liquidsemi porous membrane when placed in constant contact with an oil gelcomposition will induce oil to migrate out of the gel composition. Bythe use of gravity or oil buoyancy, no energy is required run the oilextraction process.

[0192] In the case of the invention gels of this application made in theshape of a fishing bait in contact with silicone fluid, the elastomer orrubber being highly compatible with the oil, holds the oil in placewithin the boundary of the rubber molecular phase. It is this affinityof the (i) rubber and oil molecules and (ii) the attraction of oilmolecules for each other that prevents the oil from bleeding out of thesurface of the gel body. There exist then, at the surface of the gelseveral types of surface tensions of: (iii) oil-air surface tension,(iv) oil-rubber surface tension, (v) rubber-air surface tension, (vi)rubber/oil-air surface tension, and (vii) rubber-rubber surface tension.Other forces acting on the gel are: the elastic force of the polymernetwork pulling inwards, similar to stretched out rubber bands, which isin equilibrium with the oil molecules' attraction to the rubbermolecules of the polymer network. In the case of SBS, the lowercompatibility of the midblock butadiene with oil, once a gel is made,the SBS network immediately contracts due to elastic forces to produceoil bleeding which is evidence of the poor compatibility of the rubberblock for the oil molecules.

[0193] The intermolecular forces that bind similar molecules togetherare called cohesive forces. Intermolecular forces that bind a substanceto a surface are called adhesive forces.

[0194] When two liquids are in contact such as oil and silicone fluid,there is interfacial tension. The more dense fluid is referred to hereinas the “heavy phase” and the less dense fluid is referred to as the“light phase”. The action at the surface of the oil extended polymer gelsurface when brought into contact with silicone fluid is as follows: adrop of silicone fluid when placed on the flat surface of a oil extendedpolymer gel will wet the gel surface and spread over a larger area ascompared to a drop of oil placed on the same gel surface. Because thesurface free energy of the silicone fluid in contact with the gelsurface is lower than the surface free energy of the oil, the siliconefluid has the ability to displaces the oil from the surface of the gel.

[0195] The invention gels can optionally comprise selected major orminor amounts of one or more polymers or copolymers (III) provided theamounts and combinations are selected without substantially decreasingthe desired properties. The polymers and copolymers can be linear,star-shaped, branched, or multiarm; these including: (SBS)styrene-butadiene-styrene block copolymers, (SIS)styrene-isoprene-styrene block copolymers, (low styrene content SEBSsuch as Kraton 1650 and 1652) styrene-ethylene-butylene-styrene blockcopolymers, (SEP) styrene-ethylene-propylene block copolymers, (SEPSKraton RP-1618) styrene-ethylene-propylene-styrene block copolymers,(SB)_(n) styrene-butadiene and (SEB)_(n), (SEBS)_(n), (SEP)_(n),(SI)_(n) styrene-isoprene multiarm, branched or star-shaped copolymers,polyethyleneoxide (EO), poly(dimethylphenylene oxide) and the like.Still, other (III) polymers include homopolymers which can be utilizedin minor amounts; these include: polystyrene, polybutylene,polyethylene, polypropylene and the like.

[0196] In the case of high molecular weight and combination of highstyrene content of the block copolymer which may be the reason forimprove tear and fatigue resistance, these properties may be achievedand maintained by blending (I) copolymers of SEEPS with (III) copolymersof SBS (Kraton D 1101, 1144, 1116, 1118, 4141, 4150, 1133, 1184, 4158,1401P, 4240, and KX219), SEBS (G1651, 1654).

[0197] Other (III) polymers useful in the invention gels include: oftrifluoromethyl-4,5-difuoro-1,3-dioxole and tetrafluoroethylene,polytetrafluoroethylene, maleated poly(styrene-ethylene-butylene),maleated poly(styrene-ethylene-butylene)_(n), maleatedpoly(styrene-ethylene-butylene-styrene), maleatedpoly(styrene-ethylene-propylene)_(n), maleatedpoly(styrene-ethylene-propylene-styrene), poly(dimethylphenylene oxide),poly(ethylene-butylene), poly(ethylene-propylene),poly(ethylene-styrene) interpolymer made by metallocene catalysts, usingsingle site, constrained geometry addition polymerization catalysts,poly(styrene-butadiene), poly(styrene-butadiene)_(n),poly(styrene-butadiene-styrene), poly(styrene-ethylene-butylene),poly(styrene-ethylene-butylene)_(n),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-propylene-styrene), poly(styrene-isoprene),poly(styrene-isoprene)_(n), poly(styrene-isoprene-styrene),poly(styrene-isoprene-styrene)_(n), polyamide, polybutylene,polybutylene, polycarbonate, polydimethylsiloxane; polyethylene vinylalcohol copolymer, polyethylene, polyethyleneoxide, polypropylene,polystyrene, polyvinyl alcohol, wherein said selected copolymer is alinear, radial, star-shaped, branched or multiarm copolymer, wherein nis greater than one

[0198] When the selected (III) polymers and copolymers contain greaterglassy block of styrene content of 33 and higher, such may be effectiveto provide a Gram Tack lower than a gelatinous composition having thesame rigidity formed from the (I) block copolymers and correspondingfirst plasticizers alone or the first plasticizers with a secondplasticizers. The selected component (III) polymers of polystyreneforming a styrene content of 33 and higher when used in effectiveamounts may provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the (I)block copolymers and corresponding first plasticizers alone or the firstplasticizers with a second plasticizer.

[0199] On the other hand, the lower viscosity first plasticizer canimpart lower Gram Tack to the invention gels than an increase of styrenecontent of the (I) copolymers or (III) polymers and copolymers. The lowtack and non tacky invention gels can be made from one or more linear,branched, star-shaped (radial), or multiarm block copolymers or mixturesof two or more such block copolymers having one or more midblock polymerchains which invention gels have use as articles with high tearpropagation resistance. The invention gels also possess high tensilestrength and rapid return from high extension and can exist in analtered state of delay elastomeric recovery as it regains its originalshape following high extensions or dynamic deformations. The inventiongels also exhibit low set, high dimensional stability, crack, tear,craze, and creep resistance, excellent tensile strength and highelongation, long service life under shear, stress and strain and capableof withstanding repeated dynamic shear, tear and stress forces,excellent processing ability for cast molding, extruding, fiber formingfilm forming and spinning, non-toxic, nearly tasteless and odorless,soft and strong, optically clear, highly flexible, possessing elasticmemory, substantially with little or no plasticizer bleedout, and havinglow or no tack in contact with human hand which reduction in tackinesscan be measured. The non tacky and optical properties of the inventiongels do not rely on powders or surface activation by additives toestablish their non-tackiness. The invention gels' non-tackinesspervasive the gels' entire bulk or volume. No matter how deep or inwhich direction a cut is made, the invention gels are non tackythroughout (at all points internally as well as on the gels' surface).Once the gel is cut, the invention gel immediately exhibitsnon-tackiness at its newly cut surface. Hence, the homogeneity of thenon-tackiness and optical properties of the invention gels are notknown.

[0200] Because of their improved tear resistance and resistance tofatigue, the gel compositions and s of the invention including thefluffy invention gels disclosed in U.S. Ser. No. 08/984,459(incorporated above by reference) exhibit versatility as materialsformed into hollowed thick wall body shapes for use in deep sea icewater diving or insulating the body from extreme cold. The fluffyinvention gels are advantageously useful for making one layer gloves forvibration damping which prevents damage to blood capillaries in thefingers and hand caused by handling strong shock and vibratingequipment. Of great advantage are the unexpanded particulate materialswhich can be dispersed and within a controlled temperature heating rangecan produce a predetermined volume of closed cell particulatedispersions forming the fluffy gels. The particulate materials usefulare unexpanded microspheres of poly(acrylonitrile-methacrylonitrile)copolymers encapsulated liquid isopentane which are available from AkzoNobel by the tradename Expancel. The thermoplastic microspherescomprises about 80% weight of copolymer and about 6 to about 16%isopentane and are further characterized as having a unexpanded relativedensity of about 1.2 (H2O=1.0), particle size of about 3 to about 50microns, a Tstart or softening temperature of about 106° C. to about135° C. and a decomposition or rupturing temperature Tmax of about 138°C. to about 195° C. The unexpanded thermoplastic microspheres areactivated by heat and expand to approximately about 50 times itsunexpanded size to provide an average particle density of about lessthan 0.020 specific gravity. Their lowest calculated density reached atTmax during TMA test is between about 0.25 to about 0.017 g/cm3. Morespecifically, unexpanded grades of microspheres include grades followedby (range of temperatures Tstart° C./Tmax° C.): #051 (106-111/138-147),#053 (95/102/137-145), #054 (125-135/140/150), #091 (118-126/161-171),#091-80 (118-126/171-181), and #092-120 (118-126/185-195).

[0201] The invention gels can be casted molded, pressured molded,injection molded and various methods of forming gel articles and with orwithout interlocking with various substrates, such as open cellmaterials, metals, ceramics, glasses, and plastics, elastomers,fluropolymers, expanded fluropolymers, Teflon (TFE, PTFE, PEA, FEP,etc), expanded Teflon, spongy expanded nylon, etc.; the molten inventiongel is deformed as it is being cooled. Useful open-cell plasticsinclude: polyamides, polyimides, polyesters, polyisocyanurates,polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Suitableopen-celled Plastic (sponges) are described in “Expanded Plastics andRelated Products”, Chemical Technology Review No. 221, Noyes Data Corp.,1983, and “Applied Polymer Science”, Organic Coatings and PlasticChemistry, 1975. These publications are incorporated herein byreference.

[0202] The instant gel compositions and s including fluffy gels areexcellent for cast, injection, or spinning molding and the moldedproducts have high tear resistance characteristics which cannot beanticipated form the properties of the raw components. Otherconventional methods of forming the composition can be utilized. Theinvention gel compositions and s including fluffy gel articles can beformed by blending, injection molding, extruding, spinning, casting,dipping and other conventional methods. For example, Shapes havingvarious cross-section can be extruded. The fluffy invention gels canalso be formed directly into articles or remelted in any suitable hotmelt applicator and extruded into shaped articles and films or spun intothreads, strips, bands, yams, or other shapes.

[0203] Comparisons of oil extended S-EB-S triblock copolymers have beendescribed in Shell Chemical Company Technical Bulletin SC: 1102-89(April 1989) “KRATON® THERMOPLASTIC RUBBERS IN OIL GELS” which isincorporated herein by reference.

[0204] The stearic acid and microcrystalline wax components of the gelsdescribed in my earlier U.S. Pat. No. 5,760,117 are non-sticky,invention and non-adhering. The non-adhering gels containing additivessuch as stearic acid and the like, however, feels greasy due theadditive's high solubility in oil and low melting points forming agreasy coating on the surface of the gel. The inherently invention gelswhich are an improvement over the greasy feeling gels of U.S. Pat. No.5,760,117 described above, although feels non-adhering and completelynon-tacky and non-greasy, can exhibit a high coefficient of friction orhigh COF.

[0205] I have also found that by incorporating sufficient amounts of oneor more of a selected (high melting, low oil soluble, and polar) low COFagents (such as polyphenolics with one or more sterically hinderedphenolic hydroxyl groups) in the gels will result in the appearance oflarge crystals in the interior as well as on the surface of the gels.Such crystals are shown in FIG. 5 (top view) photo of the top of ainvention gel article with phenolic crystals. These crystals have noeffect on the high COF of the resulting gels. Contrary to the combinedeffects of stearic acid and microcrystalline wax, the presence ofmicrocrystalline wax with polyphenolic in gels does not lessen the gel'sCOF and have little effect on reducing the size of the largepolyphenolic crystals. Likewise the crystallinity and glassy componentsby themselves can not by themselves reduce the inherent high COF ofthese gels. Consequently, gels containing microcrystalline wax andpolyphenolics exhibit high COF.

[0206] Surprisingly, when selected amounts of internal nucleating agentsare incorporated in the gels in combination with selected amounts of oneor more of a low COF agents, the large crystals no longer forms withinthe gels; and the surface of the gels exhibit lower and lower COF withtime. Bringing the gels in contact with selected external nucleatingagents decreases the time or totally eliminates the time needed for thegel's outer surface to exhibit a low COF. The gels and soft elastomersincorporating low COF agents and internal and/or external nucleatingagents exhibit a much lower coefficient of friction when measured incontact with a reference surface than gels and soft elastomers madewithout such components.

[0207] School book physics teaches COF can be determined experimentally,for two given surfaces that are dry and not lubricated, the ratio of thetangential force needed to overcome the friction to the normal forcewhich holds the two surfaces in contact (e.g., the weight of a block ofgel or elastomer material on a surface) is a constant, independent ofthe area or of the velocity with which the surfaces (surface of a sideof the block in contact with another surface) move over wide limits.This ratio is μ, the coefficient of friction. The coefficient of slidingfriction for a block of material being

μ=(ƒ/Fn)

[0208] where ƒ is the force of friction, and Fn the normal force. Forthe case of the block on the horizontal table, if m is the mass of theblock, then mg is the normal force and the above equation can be writtenas

μ=ƒ/mg.

[0209] In the case the block of a block rests on a board, originallyhorizontal, and that the board then is tilted until a limiting angle øis reached, beyond which the block will begin to slide down the board.At this angle the component of the weight of the object along the boardis just equal in amount to that necessary to overcome the force offriction. The force down the plane is mg sin ø, while the normal forceis mg cos ø. Therefore we have

μ=(mg sin ø)/(mg cos ø) or μ=tan ø.

[0210] The limiting value of ø for which μ=tan ø is true is call theangle of repose. Measurement of the tangent of this angle will give thecoefficient of friction of the contacting surfaces of the block and theboard that slide one upon the other.

[0211] As an example of low COF agents advantageously useful in softthermoplastic elastomers and gels, excellent results is achieved with 50grams of a polyphenolic with sterically hindered phenolic hydroxylgroups (Irganox 1010), about 100 grams of one or more nucleating agents(such as very fine particle size sodium benzoate, dibenzylidenesorbitol, its alkylated derivatives, talc, zinc sterate, amorphoussilica, aluminum sterate, etc.) and 5,000 grams of S-EB-S and 25,000gram of oil. The same excellent result is achieved when S-EB-S isadjusted to 3,000 grams, 4,000 grams, etc. The same result is achievedwith copolymers as well as in combination with other polymers. Moreover,when about 50 grams of tetrakis[methylene3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl) propionate] methane is use (perabout 22.68 Kilograms or 50 lbs of gel) as a low COF agent, tack iscompletely removed from the surface of the gel after two to three weeksof blooming.

[0212] When this is repeated with an external nucleating agent, such aswith various fine particles for coating the outside surface of theelastomer or gel, such as with talc, calcium sterate, zinc sterate,amorphous silica, aluminum sterate, fine flour, corn starch, fine soil,fine sand, fine metallic powder, vacuum dust, fine wood dusts and thelike, lower COF is achieved within a few days to less than severalhours. After coating the gel for the desired period of time, the finepolar and water soluble particles can be washed off with water and soap,while non-polar and non-water soluble fine powders can be removed bywearing it off or by lifting it off with the use of adhesive tapes if sodesired. FIG. 6. (top view) photo of the top of a invention gel articlemade with phenolics and external nucleating agents.

[0213] What is the surface properties of low CFO agents at theair/plasticizer-copolymer interface? Theory notwithstanding, theresulting gel surface will comprise of very fine molecular segments oreven very fine invention grains of low COF agents confined at theair/plasticizer and polymer interface. Depending on concentration, thenon-polar segments of the low COF agents will have a tendency of beingadsorpted by the predominate plasticizer and copolymer midblock phase atthe gel surface. The slightly polar or more polar segments of the lowCOF agents are adsorbed to a lesser extent by the plasticizer-copolymersurface. This is supported by observing the water wettingcharacteristics at the gel surface with and with out low COF agents atthe air gel surface interface. A drop of water will bead up and notreadily wet the gel surface free of any low COF agents (hydrophobic).The presence of even slightly polar low COF agents exposed on thesurface of the gel will make a drop of water flatten out and not bead upwhen place on the gel surface (hydrophilic).

[0214] Commercial high melting point, low oil solubility, and polar lowCOF agents such as polyphenolics which are advantageously useful in thepresent invention include: Ethanox 330 (Ethyl), Irganox 1010(Ciba-Geigy), Santechhem A/O 15-1 (Santech), Ultra 210 (GE), Hostanox 03(Hoechst Celanese), Irganox 3114 (Ciba-Geigy), Mixxim AO-3 (Fairmont),and the like. Other high melting point, low oil solubility, polar lowCOF agents contemplated are common amino acids: Such As Alamine;Arginine, Asparagine, Aspartic Acid, Cysteine, Glutamine, Glutamic Acid,Glycine, Histidine, Isoleucine, Leucine, Lysine, Methionine,Phenylalanine, Proline, Serine, Threonine, Tryptophan, Tyrosine andValine. The melting points of these amino acids range from about 178° C.to about 344° C., The amino acids having greater advantage serving aslow COF agents are Asparagine, Aspartic acid. Glutamine, Glutamic acid,Tryptophan, and Tyrosine. Copolymer for forming the low COF compositionsinclude block copolymers, random copolymers, metallocene catalyzedethylene-styrene copolymers, Low COF invention gels made fromthermoplastic elastomer copolymers and block copolymers having one ormore crystallizable polyethylene segments or midblocks. The low COFinvention gels advantageously exhibit high, higher, and higher, and everhigher tear resistance than realized before as well as improved hightensile strength. The low COF invention gels also exhibit improveddamage tolerance, crack propagation resistance and especially improvedresistance to high stress rupture which combination of properties makesthe gels advantageously and surprisingly suitable for use as toys,inflatable air cushions in automobiles, and the like.

[0215] The invention gels of this invention are advantageously usefulfor making low COF gel compositions. Moreover, various polymer gels madefrom linear triblock copolymers, multiarm block copolymers, branchedblock copolymers, radial block copolymers, multiblock copolymers,random/non-random copolymers, thermoplastic crystalline polyurethanecopolymers with hydrocarbon midblocks or mixtures of two or more of suchcopolymers can also be made with low COF. The COF values of theinvention gels formed form the low COF and nucleating agents are foundto be about less than 1, more advantageously less than 0.7, moreadvantageously less than 0.577, still more advantageously less than0.466 and still more advantageously less tan 0.40. The low COF inventiongels of the invention can range from less than 1.0 to about less than0.40.

[0216] As taught in my application Ser. No. 08/288,690 filed Aug. 11,1994, now U.S. Pat. No. 5,633,286 and specifically incorporated herein,additives useful in the gel of the present invention include:tetrakis[methylene 3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl) propionate]methane, octadecyl 3-(3″,5″-di-tert butyl-4″-hydroxyphenyl) propionate,distearyl-pentaerythritol-diproprionate, thiodiethylenebis-(3,5-ter-butyl-4-hydroxy) hydrocinnamate,(1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl] benzene),4,4″-methylenebis(2,6-di-tert-butylphenol), stearic acid, oleic acid,stearamide, behenamide, oleamide, erucamide, N,N″-ethylenebisstearamide,N,N″-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleylpalmitamide, stearyl stearamide, erucyl stearamide, calcium sterate,other metal sterates, waxes (e.g. polyethylene, polypropylene,microcrystalline, carnauba, paraffin, montan, candelilla, beeswax,ozokerite, ceresine, and the like). The gel can also contain metallicpigments (aluminum and brass flakes), TiO2, mica, fluorescent dyes andpigments, phosphorescent pigments, aluminatrihydrate, antimony oxide,iron oxides (Fe3O4, -Fe203, etc.), iron cobalt oxides, chromium dioxide,iron, barium ferrite, strontium ferrite and other magnetic particlematerials, molybdenum, silicone fluids, lake pigments, aluminates,ceramic pigments, ironblues, ultramarines, phthalocynines, azo pigments,carbon blacks, silicon dioxide, silica, clay, feldspar, glassmicrospheres, barium ferrite, wollastonite and the like. The report ofthe committee on Magnetic Materials, Publication NMAB-426, NationalAcademy Press (1985) is incorporated herein by reference.

[0217] The handle can be of any desired hand held shape, round, flat,thin, thick, oval made from any suitable thermoplastics,thermosetplastics, metals, ceramics materials including polypropylene,polyethylene, EVA, EA, PC, SBS, Al, SS, Ti, and the like. The inventiongels can be casted unto various substrates, such as open cell materials,metals, ceramics, glasses, and plastics, elastomers, fluropolymers,expanded fluropolymers, Teflon (TFE, PTFE, PEA, FEP, etc), expandedTeflon, spongy expanded nylon, etc.; the molten invention gel isdeformed as it is being cooled. Useful open-cell plastics include:polyamides, polyimides, polyesters, polyisocyanurates, polyisocyanates,polyurethanes, poly(vinyl alcohol), etc. Suitable open-celled Plastic(sponges) are described in “Expanded Plastics and Related Products”,Chemical Technology Review No. 221, Noyes Data Corp., 1983, and “AppliedPolymer Science”, Organic Coatings and Plastic Chemistry, 1975. Thesepublications are incorporated herein by reference.

[0218] The invention gels are prepared by blending together thecomponents including other additatives as desired at about 23° C. toabout 100° C. forming a paste like mixture and further heating saidmixture uniformly to about 150° C. to about 200° C. until a homogeneousmolten blend is obtained. Lower and higher temperatures can also beutilized depending on the viscosity of the oils and amounts ofmultiblock copolymers and polymer used. These components blend easily inthe melt and a heated vessel equipped with a stirrer is all that isrequired. Small batches can be easily blended in a test tube using aglass stirring rod for mixing. While conventional large vessels withpressure and/or vacuum means can be utilized in forming large batches ofthe invention gels in amounts of about 40 lbs or less to 10,000 lbs ormore. For example, in a large vessel, inert gases can be employed forremoving the composition from a closed vessel at the end of mixing and apartial vacuum can be applied to remove any entrapped bubbles. Stirringrates utilized for large batches can range from about less than 10 rpmto about 40 rpm or higher.

[0219] The gel compositions can also be formed directly into articles orremelted in any suitable hot melt applicator and extruded or spun intothreads, bands, or other shapes. The instant compositions is excellentfor cast molding and the molded products have various excellentcharacteristics which cannot be anticipated form the properties of theraw components. Other conventional methods of forming the compositioncan be utilized.

[0220] As taught in my application Ser. No. 08/288,690 filed Aug. 11,1994, now U.S. Pat. No. 5,633,286 and specifically incorporated herein,the gelatinous elastomer composition of the invention is excellent forforming the gelatinous elastomer articles of the invention. Thegelatinous elastomer articles can be formed by blending, melting,dipping, casting, injection molding, extruding and other conventionalmethods. For example, a foam of a preselected pore size can be placed ina mold cavity and a preselected amount of a preselected rigidity ofgelatinous elastomer composition is then injected into the mold. Themold is allow to cool to room temperature and the article removed. Apreselected rigidity of molten gelatinous elastomer composition can becast directly onto a section of open cell foam to form the article.Likewise, an article of foam can be dipped into a preselected rigidityof molten gelatinous elastomer composition and re-dipped into the sameor different composition of a different rigidity. The shaped article ofthe invention can be conventionally covered with protective skins ofelastomeric film, fabric or both as needed.

[0221] The composition can also be remelted in any suitable hot meltapplicator for hot dipping, extrusion, sputtering, or spraying on to thefoams or sponges so as to form the gelatinous elastomer articles of theinvention.

[0222] As taught in my application Ser. No. 08/288,690 filed Aug. 11,1994, now U.S. Pat. No. 5,633,286 and specifically incorporated herein,generally the molten gelatinous elastomer composition will adheresufficiently to certain plastics (e.g. acrylic, ethylene copolymers,nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F.). Commercialresins which can aid in adhesion to materials (plastics, glass, andmetals) may be added in minor amounts to the gelatinous elastomercomposition, these resins include: Super Sta-tac, Nevtac, Piccotac,Escorez, Wingtack, Hercotac, Betaprene, Zonarez, Nirez, Piccolyte,Sylvatac, Foral, Pentalyn, Arkon P, Regalrez, Cumar LX, Picco 6000,Nevchem, Piccotex, Kristalex, Piccolastic, LX-1035, and the like. Theconventional term “major” means about 51 weight percent and higher (e.g.55%, 60%, 65%, 70%, 75%, 80% and the like) and the term “minor” means 49weight percent and lower (e.g. 2%, 5%, 10%, 15%, 20%, 25% and the liketo less than 50%)(based on 100 parts of (I)).

[0223] For example, Shapes having various cross-section can be extruded.The invention gels can also be formed directly into articles or remeltedin any suitable hot melt applicator and extruded into shaped articlesand films or spun into threads, strips, bands, yarns, or other shapes.With respect to various shapes and yarn, its size are conventionallymeasured in denier (grams/9000 meter), tex (grams/1000 meter), and gage(1/2.54 cm). Gage, tex, denier can be converted as follows:tex=denier/9=specific gravity (2135/gage), for rectangular crosssection, tex=specific gravity (5806×103)(th)(w)/9, where th is thethickness and w the width of the strip, both in centimeters. Generaldescriptions of (1) block copolymers, (2) elastomeric fibers andconventional (3) gels are found in volume 2, starting at pp. 324-415,volume 6, pp 733-755, and volume 7, pp. 515 of ENCYCLOPEDIA OF POLYMERSCIENCE AND ENGINEERING, 1987 which volumes are incorporated herein byreference.

[0224] The invention gels are excellent for cast molding and the moldedproducts have various excellent characteristics which cannot beanticipated form the properties of the raw components. Otherconventional methods of forming the composition can be utilized.

[0225] Not only do the invention gels have all the desirable combinationof physical and mechanical properties substantially similar to highviscosity amorphous S-EB-S gels such as high elongation at break of1,600%, ultimate tensile strength of about 8×105 dyne/cm2 and higher,low elongation set at break of substantially not greater than about 2%,substantially about 100% snap back when extended to 1,200% elongation,and a gel rigidity of substantially from about 2 gram to about 1,800gram Bloom and higher, the invention gels of the present inventionexhibit improved tear resistance and resistance to fatigue notobtainable from amorphous S-EB-S gels at corresponding gel rigidities.

[0226] The invention gels of the present invention exhibit one or moreof the following properties. These are: (1) tensile strength of about8×105 dyne/cm2 to about 107 dyne/cm2 and greater; (2) elongation of lessthan about 1,600% to about 3,000% and higher; (3) elasticity modules ofabout 104 dyne/cm2 to about 106 dyne/cm2 and greater; (4) shear modulesof about 104 dyne/cm2 to about 106 dyne/cm2 and greater as measured witha 1, 2, and 3 kilogram load at 23° C.; (5) gel rigidity of about lessthan about 2 gram Bloom to about 1,800 gram Bloom and higher as measuredby the gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square cm at 23° C.; (6) tearpropagation resistance greater than the tear resistance of amorphousS-EB-S gels at corresponding gel rigidities; (7) resistance to fatiguegreater than the fatigue resistance of amorphous S-EB-S gels atcorresponding gel rigidities; (8) and substantially 100% snap backrecovery when extended at a crosshead separation speed of 25 cm/minuteto 1,200% at 23° C. Properties (1), (2), (3), and (6) above are measuredat a crosshead separation speed of 25 cm/minute at 23° C.

[0227] The invention gel articles molded from the invention gels haveadditional important advantages in that they end-use performanceproperties are greater than amorphous S-EP-S gels in that they are moreresistant to cracking, tearing, crazing or rupture in flexural, tension,compression, or other deforming conditions of use. Like amorphous gels,the molded articles made from the instant composition possess theintrinsic properties of elastic memory enabling the articles to recoverand retain its original molded shape after many extreme deformationcycles.

[0228] Because of their improved tear resistance and improved resistanceto fatigue, the invention gels of the present invention achieve greaterperformance than amorphous gels in low frequency vibration applications,such as viscoelastic layers in constrained-layer damping of mechanicalstructures and goods, as viscoelastic layers used in laminates forisolation of acoustical and mechanical noise, as anti-vibration elasticsupport for transporting shock sensitive loads, as vibration isolatorsfor an optical table, as viscoelastic layers used in wrappings,enclosures and linings to control sound, as compositions for use inshock and dielectric encapsulation of optical, electrical, andelectronic components.

[0229] Because of their improved tear resistance and improved resistanceto fatigue, the invention gels are more useful as molded shape articlesfor use in medical and sport health care, such use include therapeutichand exercising grips, dental floss, crutch cushions, cervical pillows,bed wedge pillows, leg rest, neck cushion, mattress, bed pads, elbowpadding, dermal pads, wheelchair cushions, helmet liner, cold and hotpacks, exercise weight belts, traction pads and belts, cushions forsplints, slings, and braces (for the hand, wrist, finger, forearm, knee,leg, clavicle, shoulder, foot, ankle, neck, back, rib, etc.), and alsosoles for orthopedic shoes. Other uses include various shaped articles,optical uses (e.g., cladding for cushioning optical fibers from bendingstresses) and various optical devices, as lint removers, dental floss,as tips for swabs, as fishing bait, as a high vacuum seal (againstatmosphere pressure) which contains a useful amount of a mineraloil-based magnetic fluid particles, safety airbags, medical bags, e.g.IV solution bags, blood bags and dialysis bags, etc.

[0230] The invention gels of the invention find use as airbags designedfor rapid deployment by expanding pressurized or ignitable gas asdescribed in my pending application U.S. Ser. No. 09/130,545 which isincorporated herein above by reference.

[0231] The various components of the airbag are denoted by: Shape of gelexpansion envelop. Gel, External retainer, internal retainer,reinforcing retainer, mechanical retainer, 8 semi integral retainer,integral pin retainer, partial external integral retainer, body, gasinlet from filter, outer sheet, inner sheet, eye retainer ring cavity,back partial integral retainer, 19 T retainer (integral reinforcing),thin gel diaphragm, thick gel diaphragm, multiple progressive thinnergel diaphragm, multiple progressive thicker gel diaphragm, multiplesingle layer expansion control elements, single layer expansion controlelements, dual single layer expansion control elements, multiple layerexpansion control elements, multiple layer diverted elements, patternedMDE, full retained gel cup, partial retained gel cup, gel cavity, S gelshaped, bulged gel, compact assembly, double layered, multiple window,double gel, baffle, gel dia., expanded, non-uniform gel dia., gelrestrainer, restrained envelope, non-uniform gel expanded mass,expansion retainer assembly, expansion control elements, dual expansiondia., single, internal and external, triple, multiple layered, tripleinternal, triple small and dural large, equal triple, dural internalwith single external surround dia., driver gel dia., enveloping driverdummy, enveloping passenger dummy, conventional air bag deployment, geland break-out pressures, gel diameter expansion final pressures.

[0232] The expansion of the gel air bag is substantially pure volumeexpansion or dilation as related to K, bulk modulus, y, young's modulus:K=y/3(1-2t), t=3k-2n/6k-2n, where t=poisson's ratio, b=1/kcompressibility=-change in V/(V• change in pressure P). Surfaceexpansion measure of air bag from initial to expanded state is from 630to 833% depending on thickness of original air bag. The initial air bagthickness can vary from 0.5 cm to 10 cms. (0.5, 1, 2, 3, 4, 5, 6, 7, 8,9, 10 cm and higher).

[0233] As disclosed in my pending patent application U.S. Ser. No.10/273,828, very thin films of the gels of the invention are suitablefor use as artificial muscles in the form of thin films wrapped into acylinder. The gel film stretch when one side of a film is given apositive charge and the other a negative. The charges cause each wrappedfilm to contract toward the center of the cylinder which forces thecylinder to expand lengthwise. When the power supply is off, thecylindrical muscles relaxes. Thus, the roll up gel can push, pull, andlift loads.

[0234] A thin films or membrane of the gels having a thickness of about5 mm to less than 0.1 mm are useful as artificial muscles. Filmthickness of from and in between: 0.005 mm, 0.01 mm, 0.02 mm, 0.03 mm,0.04 mm, 0.05 mm, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.2 mm,0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm,1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm,2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm,3.0 mm, 3.1 mm, 3.2 mm, 3.3 mm, 3.4 mm, 3.5 mm, 3.6 mm, 3.7 mm, 3.8 mm,3.9 mm, 4.0 mm can be utilized for forming artificial muscles of theinvention. Such sheets can also be use for oral dam.

[0235] Fine powder of the common transition metals can be utilized as acoating electrodes on the top and bottom flat sides of the gel film toserve as conductor, such as aluminum, alpha aluminum, copper, silver,gold, tin, nickel, iron, cobalt, zinc, lead, and the like.

[0236] We denote “|” as a gel film layer, G, and “∥” as two gel filmlayers, GG, side by side, “|∥” as three gel film layers, GGG, side byside. We denote E as a metal electrode or conductor electrode on bothsides of the G film layer, such as EGE, EGEGE, EGEGEGE, EGEGEGEGE andthe like. We denote (+) as a positive charge, (−) as a negative charge.We then denote the single charged membrane or film layer as “(+)E|E(−)”showing a single gel layer with electrodes on both sides and a positivecharge on its left side and a negative charge on its right side. Hence“(+)E|E(−)(−)E|E(+)”, denotes a double gel thin film layers withelectrodes on each side of the film layers and charged from left toright as positive, negative, negative, and positive. This arrangementallows for the rolling up of the double layers into a cylindricalcylinder without discharging the double layers by rolling unto itself.Another way of rolling up a thin gel film “(+)E|E(−)” require foldingthe ( ) side with the (−) sides as a continuous S curve layers uponlayers and then rolling the S curve so that the same charged sides rollunto itself into a cylinder. Other combination can be made for use ascharged thin film layers for artificial muscle use, such as (+)E|E(−),(+)E|E(−)(−)E|E(+), (+)E|E(−)(−)E|E(+)(+)E|E(−),(+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+), and(+)E|E(−)(−)E|E(+)(+)E|E(−)(−)E|E(+)(+)E|E(−).

[0237] Moreover, the gels films can be formed as multiple layers offilms with separating electrical conducting layer with encapsulatedconnectors for easy folding.

[0238] The diameter of the rolled up gel cylinder can be from about 1 mmto abut 8 mm, suitably, about 0.5 mm to about 5 mm, more suitably about1 mm to about 3 mm. Generally the rolled up diameter can be from lessthan 0.5 mm to about 12 mm or larger. The length of the cylinder can bealmost any suitable length, from about 5 mm to about 50 mm, suitably, 8mm to 20 mm, more suitably from less than 8 mm to 12 mm and longer.

[0239] Conductive connectors (of foil, polymer, or conductive gel) canbe attached to the inner and outer electrodes respectively. The directcurrent voltage from a regulated power supply or predetermined voltagepositive or negative potential source can be applied which voltage canrange from less than 100 volts to greater than 10,000 volts. Voltages of1,000 v, 2,000 v, 3,000 v, 4,000 v, 5,000 v, 6,000 v, 7,000 v, 8,000 v,9,000 v, 10,000 v, 12,000 v, 15,000 v, 18,000 v can also be used. Thevoltages can be regulated selectively by hand or an electronic timerfrom less than one thousands of a second to minutes, hours, and daysduration. Electrical timing of the applied voltages can range from a fewmicro seconds and longer.

[0240] The gel film can be made by conventional extrusion, hot melt spincoating, casting, dipping and the like. The artificial muscle made inthis manner are useful as contractible muscle elements for small robotswhich gel film, contracts in thickness and extends in length and widthdue to the electrostatic forces when a voltage is applied. The gelcylinder increases and decreases in volume thickness so as to expand andcontract lengthwise due to the electrostatic forces of the charges onthe opposite dielectric surfaces of the gel film. This effect is afunction of the dielectric constant of the gel. In order to provide fora muscle with a large strain and therefore a large actuation pressure(greater than 5 MPa). The performance, efficiency and faster response ofthe cylindrical muscle depends on the amount of strain obtained underelongation.

[0241] The higher strain under elongation, the better the performance,the better the efficiency, and the faster the response.

[0242] Gel muscles actuators made from thin films having greaterpolyethylene crystallinity are found to produces greater performance,greater efficiency, and faster response than amorphous gels. This resultis due to the greater strain performance under elongation. Theelongation of the gels of the invention can range from about 100% togreater than 3,000%. The actuation pressure of the actuators made fromthe gels of the invention can range from about 5 MPa to greater thanabout 12 MPa. As an example, a 15 layer rolled/folded gel film actuatorhaving a active muscle length of 10 mm and a diameter of 3 mm (made from0.5 mm thick SEEPS 500 gram Bloom gel) can achieve a stroke of about 3mm and a force of about 5 grams.

[0243] The strain under elongation of the copolymers forming the gelscan range from less than 8 MPa to about 18 MPa and higher as measure ata strain rate of 1000%/min., from less than 5 MPa to about 25 MPa andhigher as measure at a strain rate of 100%/min., and from less than 5MPa to about 30 MPa and higher as measure at a strain rate of 10%.min.Reference (19) reports the fracture strain% and corresponding modulus(Mpa) for Ethylene-styrene copolymers ES16, ES24, ES27, ES28, ES28, andES30 are 666/52.5, 517/26.4, 453/25, 564/19.5 and 468/25.4 respectively.

[0244] The ability to reduce the number of layers, increase strain withelongation, reduce the size of the active muscle actuator and increasethe stroke distance at a greater force can be achieved with gels(exhibiting high strain under elongation) made from copolymers havingone or more polyethylene components.

[0245] Moreover, the casted, extruded, or spun threads, strips, yarns,tapes can be weaned into cloths, fine or coarse fabrics. The forms ofthe invention gel yarn can be bare, double-covered, single-covered orcore plied, and core-spun. The invention gels can also be made intofibers such as side-side fibers, sheath-core fibers, multiple-segmentfibers, island-in-the-sea fibers, and matrix-fibril.

[0246] The weaned invention gels are of great advantage for formingorthotics and prosthetic articles described above because such devicesmade from weaned invention gels of fine to coarse fabrics will allow forthe human skin to breathe. The openings between weaned strands allowsfor air and oxygen transport between the skin and outer portions of thegel device body. Moreover, fine oriented or non-oriented invention gels(made from SEEBS, SEEPS, E-S-E, SEEPES, SEPEEPS and the like) in theform of threads or yarns can be produced by extruding, spinning orforced through a collection of jet nozzles to form a invention gel sprayto produce porous gel non-woven matting or webs which are skinoxygen/air breathe-able fabrics and articles. Unlike the elastomericnonwoven webs made at 290° C. of U.S. Pat. No. 4,692,371, the inventiongels must be formed advantageously below 180° C., more advantageously atabout 175° C. or lower because of the extremely high amount ofplasticizer components. If the invention gels are heated to above 200°C. and higher, the result is a puddle of hot liquid gel mass and not theporous individual form strands forming the desired fabrics. Furthermore,the invention gels are superior in properties than any gels made fromamorphous SEBS gels of substantially corresponding rigidities.

[0247] Porous, webbing or matting that are skin breathe-able comprisinginvention gel strands can be formed into a webs or matting by coldforming sandwiched invention gels strands using alkyl cyanoacrylatessuch as ethyl, butyl, methyl, propyl cyanoacrylates and the like. Thealkyl cyanoacrylates (AC) will interlock with the gels of the invention,thereby resulting in gel-(AC)-gel webbing or matting articles. Alkylcyanoacrylates are useful for interlocking invention gels of theinvention with other substrates such as pottery, porcelain, wood, metal,plastics, such as acrylics, ABS, EPDM, nylon Fiberglass, phenoics,plexiglass, polycarbonate, polyesters, polystyrene, PVC, urethanes andthe like. Other cyanoacrylates such as cyanoacrylate ester are inhibitedinterlocking with the invention gels of the invention.

[0248] The invention gels can be formed in any shape; the original shapecan be deformed into another shape (to contact a regular or irregularsurface) by pressure and upon removal of the applied pressure, thecomposition in the deformed shape will recover back to its originalshape.

[0249] As an example of the versatility of use of the invention gels, ahand exerciser can be made in any shape so long as it is suitable foruse as a hand exerciser: a sphere shape, a cube shape, a rectangularshape, etc. Likewise, a wheelchair cushion can be made from thecomposition in any shape, so long as it meets the needs of the user ofthe cushion. For example, a cushion can be made by forming thecomposition into a selected shape matching the contours of the specificbody part or body region. The composition can be formed into any desiredshaped, size and thickness suitable as a cushion; the shaped compositioncan be additionally surrounded with film, fabric, foam, or any otherdesired material or combinations thereof. Moreover, the composition canbe casted onto such materials, provided such materials substantiallymaintain their integrity (shape, appearance, texture, etc.) during thecasting process. The same applies for brace cushions, liners, liningsand protective coverings for the hand, wrist, finger, forearm, knee,leg, etc.

[0250] Because of their improved tear resistance and resistance tofatigue, the invention gels exhibit versatility as balloons for medicaluses, such as balloon for valvuloplasty of the mitral valve,gastrointestinal balloon dilator, esophageal balloon dilator, dilatingballoon catheter use in coronary angiogram and the like.

[0251] Other uses include self sealing enclosures for splicingelectrical and telephone cables and wires. For example, the inventiongels can be preformed into a small diameter tubing within an outerelastic tubing, both the internal invention gel tubing and externalelastic tubing can be axially expanded and fixed in place by a removablecontinuous retainer. Upon insertion of a spliced pair or bundle ofcables or wires, the retainer can be removed, as the retainer isremoved, the invention gel and elastic tubing impinges onto the insertedcables or wires splices, thereby sealing the electrical splices againstweather, water, dirt, corrosives and shielding the splice from externalabuse. The enclosure is completed without the use of heat or flame as isconventionally performed.

[0252] Because of their improved resistance to tearing, the inventiongels do not tear as readily as amorphous gels when used as dental floss.The dental floss can be almost any shape so long as it is suitable fordental flossing. A thick shaped piece of the composition can bestretched into a thin shape and used for flossing. A thinner shapedpiece would require less stretching, etc. For purposes of dentalflossing, while flossing between two closely adjacent teeth, especiallybetween two adjacent teeth with substantial contact points and moreespecially between two adjacent teeth with substantial amalgam alloymetal contact points showing no gap between the teeth, it is criticalthat the invention gel resist tearing, shearing, and crazing while beingstretched to a high degree in such situations. For example, dentalinvention gel floss can take the form of a disk where the segments ofthe circumference of the disk is stretched for flossing between theteeth. Other shaped articles suitable for flossing include threads,strips, yarns, tapes, etc., mentioned above.

[0253] In order for invention gels to be useful as a dental floss, itmust overcome the difficult barriers of high shearing and high tearingunder extreme elongation and tension loads. The difficulties that theinvention gels must overcome during flossing can be viewed as follows:during the action of flossing, the invention gel is stretched from noless than about 200% to about 1,100% or higher, the invention gel flossis deformed as it is pulled down with tearing action between thecontacting surfaces of the teeth, then, the wedge of invention gel flossis sheared between the inner contacting surfaces of the teeth, andfinally, the elongated wedged of invention gel floss is pulled upwardsand out between the surfaces of the teeth. The forces encountered in theact of flossing are: tension, shearing, tearing under extreme tension.

[0254] The use of invention gels advances the flossing art by providingstrong, soft, and more tear resistant gels than amorphous gels. Flossmade from the invention gels has many advantages over conventionaldental floss such as regular and extra fine waxed and unwaxed nylonfloss, spongy nylon fiber floss, and waxed and unwaxed expanded andunexpended teflon floss. Such conventional floss are not recommended foruse by children, since a slip or sudden snap in forcing the flossbetween the teeth can cause injury to the gums which often times resultsin bleeding. For sensitive gums and inflamed gums which has become redand puffy, it is difficult to floss at, near, and below the gumline. Thesoft invention gel floss with softness substantially matching thesoftness of the gums are of great advantage for use by children and forflossing teeth surrounded by sensitive and tender gums.

[0255] In all cases, the tear strength of invention gels are higher thanthat of amorphous gels. The rigidities of the invention gels for use asdental floss advantageously should be selected to exhibit a propagatingtear force (when propagating a tear as measured at 180° U bend around a5.0 mm diameter mandrel attached to a spring scale) of about 1 Kg/cm,more advantageously 2 Kg/cm, and still more advantageously of about 3Kg/cm and higher. For any gel to be considered useful for flossing, thegels should exhibit tear strengths of 2 Kg/cm and higher, advantageouslyof 4 Kg/cm and higher, more advantageously of 6 Kg/cm and higher,exceptionally more advantageously of 8 Kg/cm and higher. Typically, thetear propagation strength should range from about 5 Kg/cm to about 20Kg/cm and higher, more typically from about less than 5 Kg/cm to about25 Kg/cm and higher, especially more typically form about less than 6Kg/cm to about 30 Kg/cm and higher, and exceptionally more typicallyfrom about less than 8 Kg/cm to about 35 Kg/cm and higher.

[0256] For any gel to be considered useful for flossing, the gels,critically, should advantageously exhibit a propagating tension tearforce (when a cylindrical sample is notched and a tear is initiated atthe notched area and propagated past its maximum cylindrical diameter bylength-wise stretching of the cylindrical sample) of about 1 Kg/cm, moreadvantageously 2 Kg/cm, and still more advantageously of about 4 Kg/cmand higher. Although the invention gels of the present invention haveimproved tear resistance and resistance to fatigue greater than theamorphous gels at corresponding gel rigidities, the high and ultra-hightear resistant gels of my other related parent and c-i-p applicationstypically will exhibit even higher tear resistance values.

[0257] The invention gels of the invention can be use for making airbags. The expansion of the gel air bag is substantially pure volumeexpansion or dilation as related to K, bulk modulus, y, young's modulus:K=y/3(1-2t), t=3k-2n/6k-2n, where t=poisson's ratio, b=1/kcompressibility=−change in V/(V• change in pressure P).

[0258] Surface expansion measure of air bag from initial to expandedstate is from 630 to 833% depending on thickness of original air bag.The initial air bag thickness can vary from 0.5 cm to 10 cms. (0.5, 1,2, 3, 4, 5, 6, 7, 8, 9, 10 cm and higher).

[0259] While advantageous components and formulation ranges based on thedesired properties of the invention gels have been disclosed herein.Persons of skill in the art can extend these ranges using appropriatematerial according to the principles discussed herein. All suchvariations and deviations which rely on the teachings through which thepresent invention has advanced the art are considered to be within thespirit and scope of the present invention.

[0260] The invention is further illustrated by means of the followingillustrative embodiments, which are given for purpose of illustrationonly and are not meant to limit the invention to the particularcomponents and amounts disclosed.

EXAMPLE I

[0261] Gels of 100 parts of Kraton G1651, Kraton RP-6917 (amorphousS-EB-S), Septon 8006 (amorphous S-EB-S), Kraton RP-6918, Septon S2006,(amorphous S-EP-S) and a high viscosity radial amorphous midblocksegment (SEB)_(n) triblock copolymers and 1,600, 1,200, 1,000, 800, 600,500, 450, 300, 250 parts by weight of Duraprime 200 white oil(plasticizer having Vis. cSt @ 40° C. of 39.0) are melt blended, test,and tack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 to 1,800 gram Bloom and the tensile strength,notched tear strength, and resistance to fatigue are found to decreasewith increase amounts of plasticizers, while tackiness of the gels isfound to be greater than 7.6 gram Tack.

EXAMPLE II

[0262] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300,250 parts by weight of Duraprime 200 white oil (plasticizer having Vis.cSt @ 40° C.° C. of 39.0) are melt blended, test and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2 to1,800 gram Bloom and the gel tackiness are found to increase withincrease amounts of plasticizers and the tack greater than 7.6 gramTack.

EXAMPLE III

[0263] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Sseries poly(ethylene/styrene) random copolymer (250,000 mW) having ahigh styrene content sufficient to form gel blends with total styrenecontent of 30, 37 by weight of copolymers and 800, 600, 500, 450, 300,250 parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol,Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. ofless than 20) are melt blended, tests, and tack probe samples molded,the bulk gel rigidities are found to be within the range of 2 gram to1,800 gram Bloom and the notched tear strength and resistance to fatigueof the gel at corresponding rigidities are found to be greater than thatof amorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE IV

[0264] Gels of 100 parts of Septon 4045 (crystallizable S-E/EP-S havinga styrene content of 37.6) and 1,600, 1,200, 1,000, 800, 600, 500, 450,300, 250 parts by weight of Duraprime Klearol white oil (plasticizerhaving Vis. CSt @ 40° C. of 7-10) are melt blended, test and probesamples molded, the bulk gel rigidities are found to be within the rangeof 2 to 2,000 gram Bloom and the tackiness is found to be less thanabout 1 gram Tack.

EXAMPLE V

[0265] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of Septon2104 (Amorphous SEPS having a high styrene content of 65) and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE VI

[0266] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Mseries poly(ethylene/styrene) random copolymer (350,000 mW) having ahigh styrene content sufficient to form gel blends with total styrenecontent of 37 by weight of copolymers and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE VII

[0267] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Eseries poly(ethylene/styrene) random copolymer (240,000 mW) having ahigh styrene content sufficient to form gel blends with total styrenecontent of 37 by weight of copolymers and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE VIII

[0268] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with polystyrene homopolymers(having Mw of 3,000; 4,000; 5,000; 6,000; 7,000; 8,000; 9,000; 10,000;11,000; 12,000, 13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000;20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000; 90,000) insufficient amounts to form gel blends with total styrene content of 37,45, 48, 50, and 55 by weight of copolymers and 800, 600, 500, 450, 300,250 parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol,Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. ofless than 20) are melt blended, tests, and tack probe samples molded,the bulk gel rigidities are found to be within the range of 2 gram to2,000 gram Bloom and tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE IX

[0269] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Mseries poly(ethylene/styrene) random copolymer (350,000 mW) having ahigh styrene content sufficient to form gel blends with total styrenecontents of 40, 45, 48, 50, and 55 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I, while tack isfound to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

EXAMPLE X

[0270] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Sseries poly(ethylene/styrene) random copolymers (with Mw of 140,000;250,000 and 340,000) having a high styrene content sufficient to formgel blends with total styrene content of 40, 45, 48, 50, and 55 byweight of copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C.° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XI

[0271] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Eseries poly(ethylene/styrene) random copolymers (with Mw of 250,000;340,000 and 400,000) having a high styrene content sufficient to formgel blends with total styrene content of 40, 45, 48, 50, and 55 byweight of copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benot, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C.° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XII

[0272] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dow Mseries poly(ethylene/styrene) random copolymer (with Mw of 250,000;340,000 and 400,000) having a high styrene content sufficient to formgel blends with total styrene content of 40, 45, 48, 50, and 55 byweight of copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C.° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XIII

[0273] Gels of 100 parts of Dow E series crystallizablepoly(ethylene/styrene) random copolymer (with Mw of 250,000; 340,000 and400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 37, 40, 45, 48, 50, 55, and 60 by weightof copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C.° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

EXAMPLE XIV

[0274] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with polystyrene (of 2,500 mW, 4,000mW, 13,000 mW, 20,000 mW, 35,000 mW, 50,000 mW, and 90,000 mW;poly(alpha-methylstyrene) (of 1,300 mW, 4,000 mW;poly(4-methylstyrene)(of 72,000 mW), Endex 155, 160, Kristalex 120, and140) in sufficient amounts to form gel blends with total styrene contentof 37, 45, 48, 50, and 55 by weight of copolymers and 800, 600, 500,450, 300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C.° C. of less than 20) are melt blended, tests, and tack probesamples molded, the bulk gel rigidities are found to be within the rangeof 2 gram to 2,000 gram Bloom and tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

EXAMPLE XV

[0275] Examples XIV is repeated and gels of 100 parts of (S-EB45EP-S),(S-E-EB25S), (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S), (S-E-EP-E-S),(S-E-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-E-EP-E-EP-E-S),(S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S), and (S-E-EP-E-EP-E-S) blockcopolymers are each melt blended, tests and probe samples molded, thebulk gel rigidities are found to be within the range of 2 to 1,800 gramBloom and tack is found to decrease with decreasing plasticizer contentand in all instances substantially lower than the gels of Example I andII.

EXAMPLE XVI

[0276] Example XIV is repeated and minor amounts of 2, 5, 10 and 15parts of the following polymers are formulated with each of the triblockcopolymers: styrene-butadiene-styrene block copolymers,styrene-isoprene-styrene-block copolymers, low viscositystyrene-ethylene-butylene-styrene block copolymers,styrene-ethylene-propylene block copolymers,styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene,styrene-isoprene, polyethyleneoxide, poly(dimethylphenylene oxide),polystyrene, polybutylene, polyethylene, polypropylene, high ethylenecontent EPDM, amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole/tetrafluoroethylene. Thebulk gel rigidities of each of the formulations are found to be withinthe range of 2 gram to 2,000 gram Bloom and tack is found to decreasewith decreasing plasticizer content and in all instances substantiallylower than the gels of Example I and II.

EXAMPLE XVII

[0277] Molten gels of Examples III-XVI are formed into s with paper,foam, plastic, elastomers, fabric, metal, concrete, wood, glass,ceramics, synthetic resin, synthetic fibers, and refractory materialsand the resistance to fatigue of the -invention gels at correspondingrigidities are found to be greater than that of the amorphous gels ofExample I.

EXAMPLE XVIII

[0278] Three cm thick sheets of each of the invention gels of ExampleXIV and the amorphous gels of Example I are tested by repeatedlydisplacing the sheets to a depth of 1 cm using a 10 cm diameter smooth(water soaked) wood plunger for 1,000, 5,000, 10,000, 25,000, 50,000,and 100,000 cycles. The sheets of invention gels are found capable ofexhibiting greater fatigue resistance than the sheets of amorphous gelsat corresponding rigidities.

EXAMPLE XIX

[0279] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16 having 37.5% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XX

[0280] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES24 having 26.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXI

[0281] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES27 having 17.4% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXII

[0282] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES28 having 22.9% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXIII

[0283] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES30 having 19.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXIV

[0284] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES44 having 5.0% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples, molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample I.

EXAMPLE XXV

[0285] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES72 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVI

[0286] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES73 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55,70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVII

[0287] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES74 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXVIII

[0288] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES69 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXIX

[0289] Gels of 100 parts of Septon crystallizable (SEEPS) copolymers4033, 4055, and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES62 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example I.

EXAMPLE XXX

[0290] Gels of 100 parts of Septon (SEPS) copolymers Kraton GRP6918 incombination with each of a Dow poly(ethylene/styrene) random copolymersES16, ES24, ES27, ES28, ES30, and ES44 and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example I.

EXAMPLE XXXI

[0291] Gels of 100 parts of Septon (SEBS) copolymers S8006 and KratonG1651, G1654 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16, ES24, ES27, ES28, ES30,and ES44 and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I.

EXAMPLE XXXII

[0292] Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055,4077 in combination each with 25 parts by weight of Super Sta-tac,Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene,Zonarez, Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyal phamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXXIII

[0293] Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055,4077 in combination each with 25 parts by weight of Super Sta-tac,Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene,Zonarez, Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I.

EXAMPLE XXXIV

[0294] Gels of 100 parts of Septon (SEEPS) copolymers 4044, 4045, 4055,4077, and 4099 in combination with 1,200, 1000, 900, 800, 700, 600, 500,550 parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol,Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. ofless than 20) are melt blended, tests, the bulk gel rigidities are foundto be within the range of about 75 gram to 300 gram Bloom and havinggreater tear resistance than the SEPS gels of Example I. Such gels whenformed into composites with 1, 3, 4, 6, 7, 8, and 9 are found useful asGFGC 2 and 5 of the invention. Such rigidity gels can be formed ascomposites with the gel shapes (PRGC) of FIGS. 15a-15 k for force andpressure control and effective plaque removal.

EXAMPLE XXXV

[0295] Gels of 100 parts of Septon (SEEPS) copolymers 4044, 4045, 4055,4077, and 4099 in combination with 650, 600, 500, 550, 450, 300, 350,250, 225, 210 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, the bulk gel rigiditiesare found to be within the range of about 75 gram to 300 gram Bloom andhaving greater tear resistance than the SEPS gels of Example I. Suchgels are found useful as PRGC with rigidities 240, 260, 280, 300, 320,360, 420, 460, 480, 520, 550, 580, 620, 650, 680, 720, 750, 780, 820,850, 880, 920, 950, 980, 1,000, and above1,250. Such gels when formedinto molded shaped components as shown in FIGS. 15a-15k of the inventionare found useful as PRGC 6 of the invention.

[0296] While components and formulation ranges have been disclosedherein persons of skill in the art can extend these ranges usingappropriate material according to the principles discussed herein.Furthermore, crystallizable midblock segment block polymers can be usein blending with other engineering plastics and elastomeric polymers tomake alloyed compositions having improved impact and tear resistanceproperties. All such variations and deviations which rely on theteachings through which the present invention has advanced the art areconsidered to be within the spirit and scope of the present invention.

What I claim is:
 1. An oral care article comprising: a handle means fortransferring one or more motion forces to a plaque removing means, forcontact with a surface having attached at one end of said handle means aforce gauging means which is attached to said plaque removing means,said force gauging means for gauging said motion forces between saidplaque removing means and said surface.
 2. A force gauging meansaccording to caim 1, wherein said force gauging means is made from a gelcomposition.
 3. A force gauging means according to caim 1, wherein saidforce gauging means is made from a gel composition having a gel rigidityof about 75 gram Bloom to about 300 gram Bloom.
 4. A force gauging meansaccording to caim 1, wherein said force gauging means is made from a gelcomposition having a gel rigidity of about at least 75 gram Bloom andgreater and about at least 300 gram Bloom and lower.
 5. A plaqueremoving means according to caim 1, wherein said plaque removing meansis made from a gel composition having a gel rigidity of about at least150 gram Bloom.
 6. An oral care article comprising: a handle havingattached at one end of said handle, a gel composite of at least one gelforce gauging component and a brush member holding base, said gel forcegauging component being attached to said handle 4 and attached to saidbrush member holding base for holding a brush member opposite said gelforce gauging component, wherein said gel force gauging component ismade from a gel composition having a selected gel rigidity of about 75gram Bloom to about 300 gram Bloom.
 7. An oral care article comprising:a handle having attached at one end of said handle, a brush memberholding base, said brush member holding base being attached to at leastone gel force gauging component and holding a brush member 1 oppositesaid handle, wherein said gel force gauging component is made from a gelcomposition having a selected gel rigidity of about 75 gram Bloom toabout 300 gram Bloom.
 8. An oral care article comprising: a handlehaving attached at one end of said handle, a gel composite of at leastone gel force gauging component and a brush member holding base, saidbrush member holding base being attached to at least one gel forcegauging component 2 and holding a brush member opposite said handle,wherein said gel force gauging component is made from a gel compositionhaving a selected gel rigidity of about 75 gram Bloom to about 300 gramBloom.
 9. An oral care article comprising: a handle having attached atone end of said handle, a composite of at least one gel force gaugingcomponent and at least one plaque removing gel component, wherein saidgel force gauging component is made from a gel composition having aselected gel rigidity of from about 75 gram Bloom to about 300 gramBloom and said plaque removing gel component is made from a gelcomposition having a selected gel rigidity of from about 150 gram Bloomto about 1,250 gram Bloom.
 10. An oral care article comprising: a handlehaving attached at one end of said handle, a composite comprising atleast one gel force gauging component 5 and a plaque removing texturalcomponent, wherein said gel force gauging component is made from a gelcomposition having a selected gel rigidity of from about 75 gram Bloomto about 300 gram Bloom and said plaque removing textural component ismade from a woven or non woven fabric of webs, loops, and fibers, and asponge.
 11. An oral care article comprising: a handle having attached atone end of said handle, a plaque removing gel component, wherein saidplaque removing gel component is made from a gel composition having aselected gel rigidity of from about 75 gram Bloom to about 300 gramBloom.
 12. An oral care article comprising: a handle having attached atone end of said handle, a gel composite of at least one gel forcegauging component which is attached to at least one a plaque removinggel component, wherein said gel force gauging component is made from agel composition having a selected gel rigidity of from about 75 gramBloom to about 300 gram Bloom, and said plaque removing gel component 6is made from a gel composition having a selected gel rigidity of fromabout 150 gram Bloom to about 1,250 gram Bloom.
 13. An oral care articlecomprising: a handle attached to at least one plaque removing gelcomponent, said plaque removing gel component having an array ofprotruded shaped grooves, stems, tips, wedges, points, angular edges,corners, and sides.
 14. An oral care article comprising: a handleattached to at least one plaque removing gel component, said plaqueremoving gel component having a deep patterned surface for effectiveengaging plaque from off the surface of a tooth.
 15. An oral carearticle comprising: at least one plaque removing gel component, saidplaque removing gel component attached to a gel force gauging componenthaving a hollow member sized for receiving and holding a finger, saidgel force gauging component being surrounded by said a plaque removinggel component, wherein said gel force gauging component is made from agel composition having a selected gel rigidity of from about 75 gramBloom to about 300 gram Bloom and said plaque removing gel component ismade from a gel composition having a selected gel rigidity of from about150 gram Bloom to about 1,250 gram Bloom.
 16. An oral care articlecomprising: a gel force gauging component having a hollow member sizedfor receiving and holding a finger, said gel force gauging componentbeing surrounded by a plaque removing textural component, wherein saidgel force gauging component is made from a gel composition having aselected gel rigidity of from about 75 gram Bloom to about 300 gramBloom and said plaque removing textural component is made from a wovenor non woven fabric of webs, loops, and fibers, and a sponge.
 17. Anoral care article comprising: a gel force gauging component having ahollow member sized for receiving and holding a finger, said gel forcegauging component being surrounded by a plaque removing gel component 6,wherein said gel force gauging component is made from a gel compositionhaving a selected gel rigidity of from about 75 gram Bloom to about 300gram Bloom and said plaque removing gel component is made from a gelcomposition having a selected gel rigidity of from about 150 gram Bloomto about 1,250 gram Bloom.
 18. An oral care article comprising: a handlemeans for transferring one or more motion forces to a plaque removingmeans for contact with a surface having attached at one end of saidhandle means a gel force gauging component made from (i) 100 parts byweight of one or a mixture of two or more of a hydrogenated styreneisoprene/butadiene block copolymer(s) and from (ii) about 300 to about1,600 parts by weight of a plasticizing oil; and in combination with orwithout (iii) a selected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene.
 19. An oral care article comprising: a handle means fortransferring one or more motion forces to a plaque removing means forcontact with a surface having attached at one end of said handle means agel force gauging component made from (i) 100 parts by weight of one ora mixture of two or more of a hydrogenated styrene isoprene/butadieneblock copolymer(s) and from (ii) about 300 to about 1,600 parts byweight of a plasticizing oil; and in combination with or without (iii) aselected amount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene)_(n),poly(styrene-isoprene-styrene)_(n), poly(styrene-isoprene)_(n),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,star-shaped, branched or multiarm copolymer.
 20. An oral care articlecomprising: a handle means for transferring one or more motion forces toa plaque removing means for contact with a surface having attached atone end of said handle means a gel force gauging component made from (i)100 parts by weight of one or a mixture of two or more of a hydrogenatedstyrene block copolymer(s) with 2-methyl-1,3-butadiene and 1,3-butadieneand (ii) from about 300 to about 1,600 parts by weight of anplasticizing oil; in combination with or without (iii) a selected amountof one or more selected polymer or copolymer selected from the groupconsisting of poly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, radial,branched, star-shaped, or multiarm copolymer; and n is an integergreater than one.
 21. An oral care article comprising: a handle meansfor transferring one or more motion forces to a plaque removing meansfor contact with a surface having attached at one end of said handlemeans a gel force gauging component made from (i) 100 parts by weight ofone or a mixture of two or more of a hydrogenated styreneisoprene/butadiene block copolymer(s), wherein at least one of saidblock copolymer is a high viscosity copolymer having a viscosity valueat 5 weight percent solution in toluene at 30° C. of about 90 cps andhigher which corresponds to a viscosity at 10 weight percent of about5800 cps and higher which corresponds to a viscosity at 20 weightpercent solids solution in toluene at 25° C. of at about 80,000 cps andhigher, and (ii) from about 300 to about 1,600 parts by weight of anplasticizing oil, and in combination with or without (ii) a selectedamount of one or more polymers or copolymers ofpoly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-butylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, wherein said selected copolymer is a linear, branched,radial, star-shaped, or multiarm copolymer; and n is an integer greaterthan one.
 22. An oral care article comprising: a handle means fortransferring one or more motion forces to a plaque removing means forcontact with a surface having attached at one end of said handle means agel force gauging component made from a gel comprising a hydrogenatedstyrene block copolymer is one or more of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from less then about 75 gram Bloom toabout 300 gram Bloom and higher.
 23. An oral care article comprising: ahandle means for transferring one or more motion forces to a plaqueremoving means for contact with a surface having attached at one end ofsaid handle means a gel force gauging component made from a hydrogenatedstyrene block copolymer is one or more of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from about 75 gram Bloom to about 300gram Bloom, wherein a source of said hydrogenatedpoly(styrene-isoprene/butadiene-styrene) block polymer being a Septon®poly(styrene-ethylene-ethylene-propylene-styrene) block copolymer. 24.An oral care article comprising: a handle means for transferring one ormore motion forces to a plaque removing means for contact with a surfacehaving attached at one end of said handle means a gel force gaugingcomponent made from a hydrogenated styrene block copolymer is one ormore of a block copolymer ofpoly(styrene-ethylene-ethylene-propylene-styrene) and oil, said gelhaving a selected gel rigidity of from about 75 gram Bloom to about 300gram Bloom, wherein said one or more (i) block copolymer(s) ispoly(styrene-ethylene-ethylene-propylene-styrene) and a source of saidblock copolymers being Septon® 4033, Septon® 4044, Septon® 4045 andSepton® 4055, Septon® 4077, and Septon®
 4099. 25. An oral care articlecomprising: a handle means for transferring one or more motion forces toa plaque removing means for contact with a surface having attached atone end of said handle means a gel force gauging component made from oneor more gels made from SEBS, SEPS, SEEPS, SBS, SBEBS, SEB/EPS, silicone,and polyurethane.